Thermally processed beverage containing a fluid gel

Abstract

The present invention relates to a heat-treated beverage containing a fluid gel comprising particles formed from gellan and divalent cations, particularly calcium. The fluid gel beverage is surprisingly heat stable and maintains its suspension properties after heat treatment, including UHT (ultra-high temperature) heat treatment.

Description

[Technical Field]

[0001] The present invention relates generally to the field of beverages containing fluid gels that are stable under heat treatment, e.g., UHT treatment. For example, the present invention relates to heat-treated beverages containing fluid gels that have a specific amount of divalent cations, e.g., calcium, and are gellan-based. [Background technology]

[0002] Fluid gels are suspensions of fine particles formed from gelling polymers. Fluid gels are produced when sufficient shear force is applied to a gelling polymer solution during the gelation process. In typical gel production methods, gelation occurs by allowing the solution to gel at rest (i.e., without the application of shear or other forces).

[0003] Fluid gels are defined by the presence of a suspension of microgel particles. Fluid gels have different physical properties and dimensions than conventional (statically formed) gels. For example, fluid gels may have properties similar to those of oil droplets in emulsion-based products (see, e.g., Frith, W., Garijo, X., Foster, T., & Norton, I. (2002). Microstructural origins of the rheology of fluid gels. Special Publication - Royal Society of Chemistry). When subjected to a small (steady or oscillatory) stress, fluid gels deform in direct proportion to the stress, similar to gels formed at rest. However, above a critical stress, the deformation of fluid gels is replaced by viscous flow. This replacement contrasts with gels formed at rest, which shatter or break when a critical stress is exceeded (see Morris et al. Food Hydrocolloids; Vol. 28, No. 2, August 2012, pp. 373-411). Generally, gels formed at rest have higher moduli (G' and G'') than corresponding fluid gels (ie, formed from the same gelling agent).

[0004] Given their unique properties, there is growing interest in the use of fluid gels in the food and beverage category. For example, fluid gels can be used as fat replacers to provide a creamy mouthfeel without the calories of full-fat products. Fluid gels can also be used to provide free-flowing beverages with the ability to suspend particles within the beverage at rest.

[0005] Fluid gels and methods for producing them are known. Fluid gels are generally produced by shearing a gelling agent, such as a hydrocolloid, during gelation. The particle size and structure of the fluid gel can be tailored by adapting the production techniques and gelling agents used. For example, higher shear rates tend to produce smaller particles.

[0006] Gelling agents, such as gelling polysaccharides and gelling synthetic polymers (e.g., polymers synthesized from monomer polymerization reactions), are well known in the production of fluid gels. Gelling polysaccharides may be chemically or enzymatically modified (e.g., by deacylation-type reactions), but the polymer backbone typically remains unchanged and corresponds to naturally occurring gelling polysaccharides. Gelling polysaccharides are generally preferred over gelling synthetic polymers because they are derived from natural products and are therefore generally more acceptable by consumers and from a regulatory standpoint.

[0007] Among polysaccharides that can be used to produce fluid gels are alginate, gellan, agar, and carrageenan. Alginate is frequently used as an alginate gel, and alginate fluid gels are known to be stable to reheating after preparation. Agar, carrageenan, and gellan, which form thermoreversible gels upon cooling, are less preferred because they redissolve and lose their structure when reheated after preparation.

[0008] Heat stability is a particularly desirable characteristic for ready-to-drink beverages, such as milk, juice, or dairy products, where a pasteurization or UHT processing step is required or desirable to improve shelf life.

[0009] Pasteurization is typically carried out at temperatures below 100°C, typically between 80°C and 100°C, for longer times (compared to UHT), typically between about 30 seconds and 10 minutes. UHT (ultra-high temperature) treatment is typically carried out at higher temperatures, i.e. above 100°C, preferably above 135°C, for shorter times, for example between 2 and 90 seconds.

[0010] Alginate has been studied as a thermostable fluid gel. The thermostability of alginate gels and fluid gels is well documented.

[0011] WO 2014 / 167373A1 (Kraft Foods R&D Inc.) relates to a method for producing edible fluid gel particles for beverages. The alginate gel particles are said to be made from alginate in the presence of calcium ions and have a small particle size. The alginate gel particles are intended to replace fat in hot drinks, such as coffee and hot chocolate. The alginate gel particles are said to maintain their structure during heat treatment at temperatures up to 130°C. WO 2014 / 167373A1 explains that such thermal stability is not expected from thermoreversible gels, such as those formed from gellan.

[0012] The amount of alginate used to produce a thermostable fluid gel is relatively high, typically 0.5-5% by weight depending on the type of alginate. In WO 2014 / 167373 A1, the amount of alginate in the examples ranges from 1-4% w / w.

[0013] High amounts of gelling agents can negatively affect the sensory properties of consumer products, particularly beverages. For example, high amounts of gelling agents can result in beverages, such as cold drinks, having a strong thick or sticky mouthfeel that is not preferred by consumers. High amounts of gelling agents can also cause stickiness or mouth-coating.

[0014] It is therefore desirable to provide beverages containing fluid gels that are stable to thermal processing, particularly UHT processing, with good organoleptic properties and the ability to suspend particles, such as solid inclusions.

[0015] It is also desirable to provide beverages containing fluid gels prepared using gelling agents derived from natural sources and / or where the fluid gels are prepared using small amounts of gelling agents and / or a limited number of gelling agents.

[0016] Any reference herein to a prior art document should not be taken as an admission that such prior art is well known or forms part of the common general understanding in the art. [Summary of the Invention]

[0017] The present invention aims to improve upon the current state of the art, and in particular to provide a beverage comprising a fluid gel that overcomes the problems of the prior art and addresses the needs described above, or at least to provide a useful alternative. In particular, one object of the present invention can be to provide a beverage comprising a fluid gel that is stable under pasteurization and UHT conditions and that maintains acceptable organoleptic properties.

[0018] The inventors have surprisingly found that the object of the invention can be achieved by the subject matter of the independent claims. The dependent claims develop the inventive idea further.

[0019] Accordingly, the present invention provides a heat-treated beverage comprising a fluid gel comprising particles formed from gellan and divalent cations, e.g., divalent metal cations. The divalent cations are present at 0.001 to 0.1 wt. % based on the total weight of the beverage. The fluid gel comprising particles formed from gellan and divalent cations is present before and after heat treatment. The heat-treated beverage is a shelf-stable beverage.

[0020] The present invention also provides a method of making a beverage of the present invention. A method of making a thermally processed beverage comprising a fluid gel, comprising (preferably in order): 1. Providing a heated beverage mix comprising gellan, divalent cations, and an aqueous liquid, wherein the beverage mix comprises 0.001 to 0.1 wt. % divalent cations based on the total weight of the beverage; 2. cooling the heated beverage mixture under shear to form a cooled beverage comprising a fluid gel including particles formed from the gellan and the divalent cations; 3. heat-treating the cooled beverage containing the fluid gel to obtain a heat-treated beverage containing the fluid gel; A method comprising:

[0021] It has been surprisingly and unexpectedly discovered that fluid gels formed from gellan having certain amounts of divalent cations, such as calcium ions, are stable to heat treatment, including UHT treatment. As used herein, the term "stable" refers to the ability of a fluid gel to maintain certain properties, such as the ability to suspend particles, e.g., contained solids, during and after heat treatment.

[0022] Gellan fluid gels have been shown to be strong enough to suspend particles, such as contained solids, even at low concentrations, and even after heat treatment. Thus, the present invention provides heat-treated beverages (i.e., shelf-stable beverages) capable of suspending particles, such as contained solids, that are modifiable and have good organoleptic properties.

[0023] Gellan fluid gels maintain acceptable organoleptic properties, especially for beverage applications, even after heat treatment.

[0024] These and other aspects, features and advantages of the present invention will become more apparent to those skilled in the art from the following detailed description of the embodiments of the invention taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0025] [Figure 1] Figure 1 shows data for gellan fluid gels produced using different shear heads. Figure 1A shows the Φτ (PhiTau) values ​​for each different shear head. Figure 1B shows photographs of the different shear heads along with microscope images of the fluid gel particles. The shear head labeled "0" is the paddle in Figure 1A. Shear head "1" in Figure 1B corresponds to S1 in Figure 1A, shear head "2" in Figure 1B corresponds to S2 in Figure 1A, and so on. These are the experimental results for Example 2. [Figure 2] 1 shows a graph of Φτ versus calcium concentration for gellan and alginate fluid gels prepared in Example 3. [Figure 3] 1 shows a graph of Φτ versus pH for gellan and alginate fluid gels prepared in Example 4. [Figure 4] 4A shows graphs of viscosity versus gelling compound concentration before and after pasteurization. FIG. 4A shows the results of gellan fluid gels of various concentrations before and after pasteurization. FIG. 4B shows the results of alginate fluid gels of various concentrations before and after pasteurization. These are the experimental results of Example 5. [Figure 5]BRUCE analysis of gellan fluid gel and alginate fluid gel before and after pasteurization is shown. 5A of FIG. 5 shows the results of the gellan fluid gel before and after pasteurization. The Φτ value of the gellan fluid gel is 15.0 Pa before pasteurization and 12.1 Pa after pasteurization. 5B of FIG. 5 shows the results of the alginate fluid gel before and after pasteurization. The Φτ value of the alginate fluid gel is 7.8 Pa before pasteurization and 7.8 Pa after pasteurization. These are the experimental results of Example 5. [Figure 6] 6A and 6B show graphs of viscosity versus shear rate for fluid gels before and after UHT heat treatment. 6A shows the results for gellan fluid gels before and after UHT treatment. 6B shows the results for alginate fluid gels before and after UHT treatment. These are the experimental results for Example 5. [Figure 7] BRUCE analysis of gellan and alginate fluid gels before and after UHT treatment is shown. Figure 7A shows the results of gellan fluid gels before and after UHT treatment. The Φτ values ​​of the gellan fluid gels are 21.8 Pa before UHT and 16.9 Pa after UHT. Figure 7B shows the results of alginate fluid gels before and after UHT treatment. The Φτ values ​​of the alginate fluid gels are 5.4 Pa before UHT and 4.0 Pa after UHT. Figure 7C shows the results of gellan fluid gels made with high (0.3 wt% calcium chloride 1M) and low (0.01 wt% calcium chloride 1M) calcium solutions. The Φτ values ​​of the "low" calcium gellan fluid gels are 8.6 Pa before UHT and 20.4 Pa after UHT. The Φτ values ​​of the "high" calcium gellan fluid gels are 17.7 Pa before UHT and 10.9 Pa after UHT. These are the experimental results of Example 5. [Figure 8] 1 shows a DSC trace of the gellan fluid gel prepared in Example 5. [Figure 9]9A shows microscopic images of gellan fluid gel before and after various heat treatments. FIG. 9A shows images before and after pasteurization. Different images in each row relate to different regions of the same sample. FIG. 9B shows images before and after UHT treatment. The image on the left of FIG. 9B is before UHT treatment, and different photos in each row relate to different regions of the same sample. The image on the right of FIG. 9B is after UHT treatment, and different photos in each row relate to different regions of the same sample. These are the experimental results of Example 5. [Figure 10] 1 shows a graph of the sensory data obtained in Example 6. Specifically, the graph shows the perception of thickness as measured by a panel of various compositions of the present invention and comparative examples. The results show that the gellan fluid gel, while thicker than water, is perceived as less thick than a set gellan gel broken down into pieces afterwards, or less thick than xanthan. [Figure 11] 1 shows a graph of viscosity versus shear rate for gellan fluid gels prepared with milk before and after UHT heat treatment. These are the results of the experiment in Example 7. [Figure 12] 1 shows a graph of viscosity versus shear rate for gellan fluid gels prepared with milk at low gellan concentrations before and after UHT treatment. These are the results of the experiment in Example 7. [Figure 13] Graphs of the viscosity of two different compositions before and after heat treatment, followed by storage for 6 and 10 days, are shown. 13A of Figure 13 shows the results for a fluid gel beverage of the present invention made by adding gellan to milk. 13B of Figure 13 shows the results for a fluid gel beverage of the present invention made by adding gellan and calcium to milk. These are the experimental results for Example 8. [Figure 14]Images of various beverages containing particles are shown. In Figure 14A, the image on the right shows a heat-treated beverage containing a gellan fluid gel of the present invention, and the image on the left shows a comparative beverage without a fluid gel. The images show that, after heat treatment, fruit pieces (strawberries, blueberries, and raspberries) can be suspended in the beverage of the present invention containing a gellan fluid gel, while they cannot be suspended in the beverage without a fluid gel. Figure 14B provides further examples of different particulate matter (lime slices and fruit pieces in Figure 14A) that can be suspended in the heat-treated beverage of the present invention. The fluid gel composition in Figures 14A and 14B is 0.1% gellan + 0.05% CaCl. [Figure 15] 1 shows the results of the experiment of Example 9. [Figure 16] Figure 16 shows microscopic images of "low" and "high" calcium gellan fluid gels prepared in Example 5, before and after various heat treatments. Figure 16A shows images of the "low" calcium gellan fluid gel before and after UHT treatment. Figure 16B shows images of the "high" calcium gellan fluid gel before and after UHT treatment. Different images in each row relate to different regions of the same sample. [Figure 17] The sensory data obtained in Example 7 is shown below. DETAILED DESCRIPTION OF THE INVENTION

[0026] As used herein, the terms "comprise," "comprising," and the like are to be interpreted in an inclusive sense, i.e., "including, but not limited to," rather than in an exclusive or exhaustive sense.

[0027] As used herein, the word "about" should be understood to apply in connection with a range of numerical values. Furthermore, all numerical ranges should be understood to include each integer value within the range, where appropriate (e.g., when the range relates to a discrete feature where only integer values ​​are appropriate), and all intermediate values, where appropriate (e.g., when the range relates to a continuous feature where all intermediate values ​​are possible).

[0028] As used herein, the singular articles "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0029] As used herein, the term "substantially free" means that the excluded material is present in an amount of less than 10 weight percent, preferably less than 5 weight percent, and more preferably less than 1 weight percent. In a preferred embodiment, "substantially free" means that no more than 0.1 weight percent of the excluded material remains. "Completely free" typically means that only trace amounts of the excluded material are present, and preferably no detectable amounts are present.

[0030] As used herein, the term "having a shelf life of at least two months" means that the thermally processed beverage will not spoil over a two month period of storage under ambient and / or refrigerated conditions.

[0031] As used herein, "plant-based milk substitute" refers to a food product that contains plant-derived ingredients, is dairy-free, and has similar qualities in appearance and texture to the corresponding real dairy milk. Preferably, the milk analog is made only from vegan ingredients.

[0032] As used herein, the term "vegetarian" refers to an edible composition that does not contain meat, such as fish.

[0033] As used herein, the term "vegan" refers to an edible composition that does not contain any animal products or animal-derived products.

[0034] Unless otherwise stated, all percentages herein refer to weight percentages, where applicable.

[0035] Unless otherwise defined, all technical and scientific terms have the same meaning and should be given the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0036] The present invention provides a heat-treated beverage comprising a fluid gel containing particles formed from gellan and divalent cations, e.g., divalent metal cations. The divalent cations are present in an amount of 0.001 to 0.1 wt. % based on the total weight of the beverage. The fluid gel containing particles formed from gellan and divalent cations is present both before and after heat treatment. The heat-treated beverage is shelf-stable.

[0037] By "shelf stable" it is understood that the thermally processed beverage has a shelf life of at least 1 week, for example at least 1 month, for example at least 3 months, or at least 6 months, preferably 1-12 months, more preferably 3-12 months, and even more preferably 6-12 months, when stored under storage conditions, for example, ambient and / or refrigerated conditions; preferably, the thermally processed beverage has such a shelf life when stored under ambient conditions. The term "ambient conditions" refers to a temperature in the range of 15°C to 25°C, preferably 20°C to 22°C, and in particular a pressure of about 1 atmosphere. The term "refrigerated conditions" refers to a temperature in the range of 0°C to 15°C, preferably 1°C to 5°C, and in particular a pressure of about 1 atmosphere. These storage temperatures relate to the storage of the composition before purchase by the end consumer. Generally, the end consumer is advised to store the composition under the same conditions, for example, at room temperature and pressure, on a shelf until consumption. In some cases, the term "shelf-stable" is also used to refer to a "shelf-stable" beverage. As used herein, "shelf-stable" can also refer to the property that the thermally processed beverage is stable upon storage as outlined above, e.g., the beverage maintains its ability to suspend particles, e.g., contained solids, during storage.

[0038] The thermally treated beverage may be a dairy beverage, a plant-based dairy beverage substitute, a coffee beverage, a cocoa beverage, a malt beverage, a tea, a juice, a soft drink, or a mixture thereof.

[0039] A heat-treated beverage refers to a beverage that has undergone a heat treatment process, such as pasteurization or UHT treatment, to extend the shelf life of the beverage. The heat treatment can be carried out at 80°C or higher, for example 90°C or higher, preferably 100°C or higher, preferably 120°C or higher. The heat treatment can be carried out at 160°C or lower, for example 150°C or lower, preferably 140°C or lower. The heat treatment can be carried out within a temperature range taken from the above upper and lower limits. For example, the heat treatment can be carried out at 80 to 160°C, preferably 100 to 140°C.

[0040] The fluid gel used in the beverage is stable when subjected to heat treatment. That is, a fluid gel comprising particles formed from gellan and divalent cations is present in the beverage before and after heat treatment. The fluid gel formed from gellan survives the heat treatment process to provide the heat-treated beverage of the present invention. In some cases, the physical properties of the gellan-based fluid gel can be substantially the same before and after heat treatment.

[0041] In this way, the present invention provides at least an alternative fluid gel (to the heat-resistant alginate fluid gels of the prior art) that can be heat treated, e.g., UHT treated, without significantly affecting the properties of the fluid gel.

[0042] The present invention also provides a fluid gel beverage that is heat stable and can suspend particles, such as solids, even at low gelling agent concentrations. The ability to use a wide range of gelling agent amounts (including smaller amounts) means that the beverage of the present invention can have controlled sensory characteristics to suit specific applications. Also, the amount of gelling agent used can be reduced.

[0043] The present invention also provides a method for producing a thermally processed beverage comprising a fluid gel, the method comprising: providing a beverage mix comprising gellan, divalent cations, and an aqueous liquid, the beverage mix comprising 0.001 to 0.1 wt. % divalent cations based on the total weight of the beverage; heating the beverage mixture to obtain a heat-treated beverage mixture; cooling the heat-treated beverage mixture under shear to form a beverage comprising a fluid gel formed from the gellan and the divalent cations; heat-treating the beverage comprising the fluid gel to obtain a heat-treated beverage comprising the fluid gel; The present invention provides a method comprising:

[0044] Gellan is a well-known gelling agent and has been studied for its ability to form fluid gels. Gellan fluid gels are generally discussed in Sworn et al. ("Gellan gum fluid gels; Food Hydrocolloids, Vol. 9, no. 4, pp. 265-271) where Sworn et al. investigate the properties of gellan fluid gels. The test solutions used in the study are prepared using a rheometer. Fluid gels are formed using 0.125 wt. % gellan in the absence of cations, using sodium, and using calcium. Sworn et al. do not heat treat these test solutions after the fluid gels are formed, and there is no discussion of the heat treatment or heat resistance of the fluid gels. Gellan is generally considered to be thermally unstable, and heating is known to destroy the gel structure (see WO 2014 / 167373 A1 and Gelation of Gellan-A review, Food Hydrocolloids, Vol. 28, Issue 2, pp. 373-411).

[0045] Surprisingly and unexpectedly, the gellan fluid gel in the heat-treated beverage of the present invention has been shown to be stable during pasteurization and UHT treatment. As used herein, stability refers to the maintenance of one or more properties, particularly the ability to suspend particles, e.g., contained solids, before and after heating. Furthermore, the gellan fluid gel of the present invention has been shown to be more stable than the corresponding alginate fluid gel prepared at a similar concentration.

[0046] The use of gellan to form the fluid gels of the present invention results in a more controlled formulation compared to alginate, which is known to react quickly to produce irregular particles.

[0047] The fluid gel of the beverage of the present invention also provides the advantage that less gelling agent can be used and still achieve the desired suspension properties, so that the viscosity of the overall beverage can be tailored to suit the end user and aid in the manufacturing process.

[0048] The heat-treated beverage contains an aqueous liquid. The aqueous liquid may be selected from the list consisting of water, coffee, tea, cocoa-based beverages (e.g., hot chocolate), malt-based beverages, fruit juice, vegetable juice, milk, plant-based milk substitutes, soup, or a mixture thereof. The heat-treated beverage of the present invention may also contain any other ingredients known in beverages. For example, the heat-treated beverage of the present invention may contain minerals, salts, buffer salts, flavors, colorants, carbohydrates, fats, proteins, preservatives, stabilizers, probiotics, prebiotics, and vitamins. Carbohydrates include sugars, sweeteners, and fiber.

[0049] The heat-treated beverage of the present invention may further contain solids. Solids are compounds that are immiscible with the heat-treated beverage and remain visible to the naked eye when dispersed in particulate form in the heat-treated beverage. These solids are preferably uniformly suspended in the heat-treated beverage. The solids may be chocolate chips, citrus peel, fruit pieces, vegetable pieces, candied fruit, dried fruit, confectionery pieces, spices, nuts, vanilla granules, ground vanilla pods, tapioca balls, polysaccharide-based beads, or mixtures thereof. An example of polysaccharide-based beads is alginate beads. The solids may be particulate matter, such as sediment, for example, cocoa powder.

[0050] Fluid Gel The heat-treated beverage of the present invention comprises a fluid gel comprising particles formed from gellan and 0.001 to 0.1 wt % divalent cations based on the total weight of the beverage.

[0051] In some cases the particles fill 25-75%, preferably 40-60%, for example about 50% of the total volume of the beverage.

[0052] In some cases, the concentration of gellan in the particles is 1 to 3 times the concentration of gellan in the beverage, for example, the concentration of gellan in the particles is about 2 times the concentration of gellan in the beverage.

[0053] The term fluid gel, as used herein, refers to a gel that flows when poured and remains cohesive upon standing. Fluid gels are compositions in which the bulk shear properties of the effective medium (i.e., the gel suspension) differ from the bulk shear properties, particularly the elasticity and yield stress properties, of the individual microgel particles. These fluid gel properties can be measured by atomic force microscopy (AFM) or the BRUCE method described herein. For example, fluid gels can be identified based on a BRUCE shear yield stress that is different from the shear yield stress measured by bulk shear rheometry. BRUCE shear yield can be measured as outlined in the experimental section using conventional techniques known to those skilled in the art.

[0054] As used herein, "bulk shear rheometry" refers to standard rheometry techniques known in the art for measuring shear yield stress. For example, shear yield stress can be measured using bulk shear rheometry by performing strain sweep tests from 0.1 to 1000% strain at 1 Hz using an Anton Paar rheometer, MCR series, equipped with a CC27 Sanded geometry, measured at 20°C.

[0055] Fluid gels are formed by applying a sufficiently energetic flow field, e.g., by shear, to a gelling agent in solution while it undergoes a conformational transition and consequent cohesion, i.e., during gel hardening. Typically, the flow field is applied using a rheometer or shear mixer during the cooling process. Fluid gels can be referred to as structured liquids or weak gels. Fluid gels can be described as wet, soft granular materials or soft microgel particle suspensions. Fluid gels contain particles formed from a gelling material (e.g., gellan) suspended in a bulk solvent phase, e.g., an aqueous liquid. The gel particles provide the structural properties of the fluid gel.

[0056] The fluid gel of the beverage of the present invention comprises particles formed from gellan and a divalent cation, such as calcium, i.e., the particles of the fluid gel are composed of gellan polysaccharide chains cross-linked to one another by a divalent cation, such as calcium.

[0057] The fluid gel beverages of the present invention may have a balanced set of properties. This balance of properties may provide a beverage with desired characteristics. The desired characteristics may vary depending on the type of beverage. For example, for some beverages, desired characteristics may include pourability / drinkability, the ability to suspend solid particles, and a clean mouth feel (e.g., no particles), as well as a viscosity that is low enough to be palatable (e.g., not as thick as a smoothie).

[0058] In some embodiments, the beverages of the present invention have a pH of at least 3, e.g., at least 3.5, preferably at least 4. In some embodiments, the beverages of the present invention have a pH of 3 to 8, e.g., 3.5 to 7, preferably 4 to 7. The pH may be measured using a pH probe at 20°C. The pH probe may be a handheld pH probe with gel electrolyte, e.g., a Ph110 pH meter from VWR. The pH probe may be calibrated the same day. The pH may be measured after complete solubilization of the hydrocolloid.

[0059] Without wishing to be bound by theory, it is believed that the pH of the beverage may affect the binding between gellan and divalent cations and therefore affect the fluid gel properties. The pH is preferably selected to provide optimal properties, such as calcium binding, viscosity, and / or the ability to suspend particles in the beverage even after heat treatment.

[0060] In some embodiments, particles formed from gellan and divalent cations in a fluid gel have a particle size of 10-1000 μm, for example, 20-500 μm, preferably 30-100 μm.

[0061] As used herein, particle size refers to the volume average particle size. Particle size can be measured by microscopy and visual inspection. For example, a microscopic image can be taken using an Axioplan microscope. The maximum dimensions of 2 to 5 particles in the image are measured visually using a scale bar, and the average is calculated. Images can be stained before analysis, for example, with toluidine blue.

[0062] The particles of the fluid gel have a variety of sizes (i.e., they are not completely uniform or identical in size). In some embodiments, the particle sizes of the fluid gel particles discussed above refer to volume-based particle sizes between d10 and d90. That is, the particle sizes are those particle sizes between the 10th percentile (i.e., d10) and the 90th percentile (i.e., d90) of the overall particle size distribution.

[0063] Fluid gels having the above particle sizes can be prepared by adjusting production parameters, as is well known in the art. For example, it is well known that the cooling rate, shear rate, and type of paddle affect the particle size and distribution of fluid gels. In particular, for preferred particle sizes, a mixer capable of high shear rates can be used to produce the desired fluid gel. Suitable mixers include a Ystral mixer, a Mondomix pin stirrer, and a Silverson L5M-A. Fluid gels produced using a rheometer have larger particle sizes, for example, greater than 500 μm.

[0064] In this way, the beverage of the invention has good thermostability properties towards thermal treatments in combination with good organoleptic properties and can be produced on an industrial scale.

[0065] The viscosity of the fluid gel beverage changes depending on the shear rate. At low shear, the viscosity of the fluid gel can be relatively high, and at high shear, the viscosity is much lower. In this way, when the fluid gel beverage is at rest (e.g., low shear), the fluid gel beverage has the ability to support particles, and when the fluid gel beverage is consumed (e.g., high shear), the fluid gel beverage pours and behaves like a regular beverage.

[0066] In one embodiment, the fluid gel beverage has a viscosity of at least 10 mPa.s, at least 100 mPa.s, at least 500 mPa.s, preferably at least 1,000 mPa.s, measured at a shear rate of 0.1 1 / s in a steady shear measurement.

[0067] In one embodiment, the fluid gel beverage has a viscosity in a steady shear measurement of at most 30,000 mPa.s, at most 20,000 mPa.s, preferably at most 10,000 mPa.s, measured at a shear rate of 0.1 1 / s.

[0068] In one embodiment, the fluid gel beverage has a viscosity in the range of 100 to 15,000 mPa.s, such as 1,000 to 10,000 mPa.s, measured at a shear rate of 0.1 1 / s.

[0069] In one embodiment, the fluid gel beverage has a viscosity of at least 1 mPa.s, at least 5 mPa.s, preferably at least 10 mPa.s, measured at a shear rate of 100 1 / s in a steady shear measurement.

[0070] In one embodiment, the fluid gel beverage has a viscosity in a steady shear measurement of at most 1000 mPa.s, at most 500 mPa.s, preferably at most 100 mPa.s, measured at a shear rate of 100 1 / s.

[0071] In one embodiment, the fluid gel beverage has a viscosity in the range of 1 to 1000 mPa.s, for example 10 to 1000 mPa.s, measured at a shear rate of 100 1 / s. Viscosity as discussed herein may refer to the viscosity of the heat-treated beverage after heat treatment.

[0072] In one embodiment, the fluid gel beverage has a viscosity at 0.1 1 / s and a viscosity at 100 1 / s, as defined above. In particular, the fluid gel beverage has a viscosity in the range of 1,000 to 10,000 mPa.s, measured at a shear rate of 0.1 1 / s, and the fluid gel beverage has a viscosity in the range of 10 to 100 mPa.s, measured at a shear rate of 100 1 / s.

[0073] Viscosity as discussed herein may refer to the viscosity of the heat-treated beverage after heat treatment. Viscosity values ​​may be measured at 20°C using steady shear measurements. For example, viscosity may be measured using an Anton Paar rheometer, MCR series, equipped with a CC27 sanding geometry. The applied shear rate may be between 0.01 and 300 s. -1 Starting at 1000 kJ / s, data points can be recorded for each decade. Such measurements are described in the examples of the present invention, and exemplary results are shown in Figures 4, 6, 11, and 12.

[0074] In one embodiment, the fluid gel beverage has a Φτ value of at least 4 Pa, such as at least 10 Pa, preferably at least 20 Pa.

[0075] In one embodiment, the fluid gel beverage has a Φτ value of at most 100 Pa, such as at most 75 Pa, preferably at most 60 Pa.

[0076] In some embodiments, the Φτ value of the fluid gel beverage is within a range taken from either of the upper and lower limits described above. For example, the Φτ value of the fluid gel beverage may be 10 to 75 Pa, preferably 20 to 60 Pa.

[0077] As used herein, the term "Φτ (PhiTau)" is a shorthand notation for compound parameters consisting of yield stress (τ, Tau) and packing fraction (φ, Phi). In particular, Φτ is the parameter: 2xφPhi (2 / 3) xTau Used to refer to

[0078] τ (Tau) is the shear yield stress and φ (Phi) is the bulk volume fraction of gel particles.

[0079] Φτ provides a quantitative measure of the ability of a fluid gel to support particles at a given concentration, with higher Φτ values ​​indicating that the fluid gel is more able to support particles.

[0080] Φτ can be measured by the BRUCE method, as outlined in detail in the Examples section. Preferably, Φτ is measured at 20°C. Conventional shear rheometry processes, when applied to fluid gels, measure the (weaker) stress between discrete fluid gel particles. This is because the fluid gel particles can rotate relative to each other without deformation in this type of shear experiment. The BRUCE method measures the true yield stress of the fluid gel particles, which are destroyed in the measurement process.

[0081] For normal continuous gels without particles (e.g., those produced under quiescent conditions), shear yield stress measurements performed using bulk shear rheometry (described above) should provide the same τ value as measurements provided by the BRUCE method. Using bulk shear rheometry and BRUCE measurements on fluid gels will result in different shear yield stress (τ) values ​​because they measure different physical properties. To obtain τ values ​​from BRUCE measurements, φ values ​​are estimated at approximately 50% loading based on the literature on powder packing. Alternatively, τ for fluid gels can be obtained directly by atomic force microscopy (AFM).

[0082] A high Φτ value (e.g., 10-75 Pa, preferably 20-60 Pa), low viscosity at rest (e.g., 1,000-10,000 mPa.s measured at a shear rate of 0.1 1 / s) and high viscosity upon pouring (e.g., 10-100 mPa.s measured at a shear rate of 100 1 / s) are a preferred combination of physical properties for beverage products containing fluid gels.

[0083] Gelan The beverage of the present invention comprises a fluid gel containing particles formed from gellan.

[0084] Gellan, also known as gellan gum, refers to a product derived from an extracellular polysaccharide produced by fermentation of the organism Sphingomonas (formerly Pseudomonas elodea). The polysaccharide that forms the basis of gellan has a repeating unit consisting of two residues of D-glucose and one residue each of L-rhamnose and D-glucuronic acid. Gellan products can be prepared by chemically modifying the polysaccharide produced by fermentation, for example, by diacylation of the side chains. Generally, chemical modifications affect the side chain groups, leaving the polysaccharide backbone intact. Gellan products are generally divided into two categories: low-acyl and high-acyl, depending on the number of acetate groups attached to the polymer.

[0085] Gellan is also known as gellan gum. Gellan is classified as E418 (Standard Food Additive Number) or [D-Glc(β1→4)D-GlcA(β1→4)D-Glc(β1→4)L-Rha(α1→3)] n It is sometimes called.

[0086] In some embodiments, the gellan is a divalent cation-responsive gellan. By "divalent cation-sensitive gellan" is understood a gellan whose gelation is regulated and / or induced by the presence of divalent cations, particularly the divalent cations disclosed herein.

[0087] In some embodiments, the gellan used in the present invention is low-acyl gellan. For example, the gellan may have less than 50% acylation, preferably less than 25% acylation. In some embodiments, the gellan has more than 1% acylation, preferably more than 10% acylation. The acylation of the gellan may be within a range taken from the upper and lower limits set forth above. For example, the gellan may have an acylation of 1 to 50%, preferably 10 to 25%.

[0088] This can increase cross-linking between gellan and divalent cations, such as calcium, and improve temperature resistance.

[0089] In some embodiments, the gellan has a molecular weight, such as an average molecular weight of 100,000 to 500,000 Da, preferably 200,000 to 300,000 Da.

[0090] In some embodiments, the concentration of gellan in the beverage is at most 1.0 wt.%, such as at most 0.8 wt.%, for example at most 0.6 wt.%, such as at most 0.15 wt.%, for example at most 0.12 wt.%, such as at most 0.11 wt.%, preferably at most 0.10 wt.%, based on the total weight of the beverage.

[0091] In some embodiments, the concentration of gellan in the beverage is at least 0.01 wt.%, such as at least 0.03 wt.%, for example at least 0.04 wt.%, such as at least 0.08 wt.%, preferably at least 0.05 wt.%, based on the total weight of the beverage.

[0092] In some embodiments, the concentration of gellan in the beverage is within a range taken from either of the above upper and lower limits. For example, the amount of gellan in the beverage may be 0.05 to 0.5 wt. %, such as 0.08 to 0.11 wt. %, preferably 0.04 to 0.11 wt. %, based on the total weight of the beverage.

[0093] The concentration of gellan can be used to tailor the properties of the beverage. For example, at higher concentrations, the thickening effect of free gellan can increase the viscosity of the bulk solvent phase, making it more difficult to shear to produce a fluid gel. It would be desirable to be able to use varying amounts of gellan (or any gelling agent) and still provide beneficial properties (e.g., particle or solid content suspension ability, good organoleptic properties) because this allows for the use of an amount suitable for providing the desired viscosity in the final product. For example, prior art UHT-stable alginate fluid gels have much higher concentrations (approximately 1-4 wt. % alginate) that result in more viscous beverages, making them of limited utility (i.e., limited to beverages intended to be viscous) and lacking optimal organoleptic properties.

[0094] In this way, the above concentration ranges are proposed to provide the beverage with sufficient yield stress properties to suspend particles, while also limiting viscosity so that the beverage has a desired flow consistency when shear is applied (e.g., by pouring).

[0095] The fluid gel of the beverages of the present invention comprises particles formed from gellan and divalent cations. In some cases, the fluid gel particles may also be formed from additional components, such as other gelling agents or aqueous liquids. That is, the fluid gel particles may be formed from gellan, divalent cations, and other components.

[0096] In some embodiments, the fluid gel particles consist solely of gellan and divalent cations. That is, the fluid gel particles are formed solely from gellan and divalent cations. In other words, the fluid gel particles are substantially free of any other gelling agents different from gellan. Preferably, the fluid gel particles are completely free of any other gelling agents different from gellan. For example, the fluid gel particles do not contain any of the following gelling agents: xanthan gum, alginate, agar, carrageenan, furcellaran, colloidal microcrystalline cellulose (colloidal MCC), tamarind seed gum, locust bean gum (LBG), tragacanth gum, pectin, konjac, curdlan, guar gum, and gelatin.

[0097] The fluid gel particles may be free of any of these other gelling agents different from gellan. However, gelling agents different from gellan may be present in the bulk beverage, for example, to act as thickeners or to provide solids content (e.g., alginate beads). In one embodiment, the heat-treated beverage is substantially free of any of these other gelling agents different from gellan, and preferably, the heat-treated beverage is completely free of any of these other gelling agents different from gellan.

[0098] cation The beverage of the present invention comprises a fluid gel containing 0.001 to 0.1% by weight of divalent cations, based on the total weight of the beverage.

[0099] Without being bound by theory, it is believed that divalent cations act to cross-link gellan polymer chains, providing microgel particles in solution. In particular, divalent cations are believed to stabilize gellan by adding electrostatic stabilization to the folded helices. It is also believed that the inclusion of some divalent cations allows gellan to form fluid gels at lower concentrations than would be possible with gellan alone.

[0100] The term divalent cation refers to a positively charged species having a 2+ charge.

[0101] In some embodiments, the divalent cation can be a divalent metal cation. In some embodiments, the divalent metal cation is selected from calcium, magnesium, zinc, copper, iron, or mixtures thereof. Preferably, the divalent metal cation is calcium (Ca 2+ )

[0102] In some embodiments, the divalent metal cations are provided by the addition of a metal salt. Preferably, the metal salt is soluble. Examples of soluble metal salts include calcium chloride hydrate (i.e., CaCl(H2O) n (where n is 1 to 5, preferably n is 2), calcium acetate hydrate (i.e., CaOAc·H2O), calcium lactate hydrate (e.g., pentahydrate), calcium glycerophosphate, tricalcium citrate tetrahydrate, or calcium sulfate. Preferably, the metal salt is calcium chloride hydrate (i.e., CaCl2·(H2O) n (wherein n is 1 to 5, preferably n is 2), calcium acetate hydrate (i.e., CaOAc·H2O), calcium lactate hydrate (e.g., pentahydrate), and calcium glycerophosphate. More preferably, the metal salt is calcium chloride hydrate, e.g., calcium chloride dihydrate.

[0103] pH can affect the solubility of metal salts. In some embodiments, the metal salts can have a solubility of at least 10 mM in water at 20° C. and pH 7, preferably at least 100 nM, preferably at least 200 nM in water at 20° C. and pH 7.

[0104] The sparingly soluble or insoluble metal salts can be used in combination with a hydrolysis agent, such as a slow hydrolysing or slow-release acid, such as GDL or a fat-coated acid.

[0105] In some embodiments, the amount of divalent cations, preferably calcium, in the beverage is at most 0.06 wt. %, such as at most 0.04 wt. %, preferably at most 0.03 wt. %, based on the total weight of the beverage.

[0106] In some embodiments, the amount of divalent cations, preferably calcium, in the beverage is at least 0.001 wt. %, such as at least 0.003 wt. %, for example at least 0.006 wt. %, such as at least 0.01 wt. %, preferably at least 0.02 wt. %, based on the total weight of the beverage.

[0107] In some embodiments, the amount of divalent cations, preferably calcium, in the beverage is within a range taken from any of the above upper and lower limits. For example, the amount of divalent cations, preferably calcium, in the beverage may be 0.001 to 0.06 wt. %, preferably 0.01 to 0.04 wt. %, based on the total weight of the beverage.

[0108] In this way, the fluid gel exhibits good physical properties for beverages, such as low viscosity, while maintaining the ability to suspend particles even after heat treatment. In particular, within the above-mentioned divalent cation content range, it is believed that the amount of crosslinking formed between the divalent cations and gellan is optimal to ensure that the fluid gel has an optimized viscosity and remains stable after heat treatment. Without being bound by theory, it is believed that a low concentration of divalent cations, especially calcium, results in a low amount of crosslinking, leaving gellan in the bulk aqueous liquid, which increases viscosity, while a high content of divalent cations, preferably calcium, is thought to saturate binding sites, thereby reducing crosslinking efficiency.

[0109] In some embodiments, other beverage ingredients may contain divalent cations, particularly calcium, and therefore no additional divalent cations, particularly calcium, need be added. For example, if the beverage contains milk or plant-based milk (e.g., oat milk) as an aqueous liquid or other dairy ingredient that contains the required level of calcium, no additional calcium needs to be added to provide a beverage of the present invention.

[0110] process The present invention also provides a method for producing the thermally treated beverage of the present invention.

[0111] 1. A method for producing a thermally processed beverage comprising a fluid gel, preferably comprising the steps of: 1. Providing a heated beverage mix comprising gellan, divalent cations, and an aqueous liquid, the beverage mix comprising 0.001 to 0.1 wt. % divalent cations based on the total weight of the beverage; 2. cooling the heated beverage mixture under shear to form a cooled beverage comprising a fluid gel including particles formed from the gellan and the divalent cations; 3. heat-treating the cooled beverage containing a fluid gel to obtain a heat-treated beverage containing a fluid gel, in particular a heat-treated beverage containing a fluid gel comprising particles formed from gellan and divalent cations; A method comprising:

[0112] The heat treatment step (step 3 above) may be pasteurization or UHT heat treatment. In some embodiments, the heat treatment step may involve heating the beverage mixture to a temperature of 80-145°C, preferably 100-140°C, even more preferably 120-140°C.

[0113] In some embodiments, the heat treatment step (step 3 above) may involve heating for at least 2 seconds, preferably at least 3 seconds, e.g., about 5 seconds. In some embodiments, the heat treatment step may involve heating for up to 90 seconds, preferably up to 40 seconds, more preferably up to 30 seconds, and even more preferably up to 7 seconds.

[0114] The step of preparing a heated beverage mix (step 1 above) may include heating the beverage mix to 60-90°C, preferably 70-80°C. Heating may be performed before or after adding calcium to the beverage mix. The heating step may be performed before or after adding gellan to the beverage mix. Preferably, the aqueous liquid is heated, then gellan is added, followed by calcium, before the shearing step (step 2). During the heating step, the gellan may be hydrated.

[0115] The shearing step (step 2 above) is preferably carried out at a high shear rate. For example, the shear rate may be 400 to 10,000 rpm, preferably 500 to 800 rpm or 4000 to 8000 rpm. The shearing step may also be carried out by shearing through a nozzle.

[0116] Cooling (step 2 above) may be carried out at a temperature of from 80-90°C to 15-25°C, for example, from 60-70°C to 18-22°C.

[0117] Various shearing methods and various cooling rates can be used to tailor the particle size of the fluid gel. The gellan-based fluid gels of the present invention have been found to be surprisingly heat stable over the range of particle sizes produced.

[0118] Additional beverage ingredients not mentioned in step 1 above may be added at any point between steps 1 and 2. That is, additional beverage ingredients may be added after the fluid gel is formed (i.e., after step 2) and before the heat treatment step (step 3).

[0119] The preferences provided above for the heat-treated beverage aspects of the invention apply equally to the method claims, where relevant, e.g., the amount of gellan disclosed for the heat-treated beverage may be the same in the method.

[0120] Those skilled in the art will understand that all features of the invention disclosed herein can be freely combined. In particular, features described with respect to the product of the invention can be combined with the method of the invention, and vice versa. Furthermore, features described with respect to different embodiments of the invention may be combined.

[0121] Furthermore, where known equivalents exist for specific features, such equivalents are incorporated as if specifically referred to herein. Further advantages and features of the present invention will be apparent from the drawings and non-limiting examples.

[0122] Numbered clauses The following numbered clauses provide embodiments of the present invention.

[0123] 1. A heat-treated beverage comprising a fluid gel containing particles formed from gellan and divalent cations, wherein the divalent cations are present at 0.001 to 0.1% by weight based on the total weight of the beverage. 2. The thermally treated beverage of clause 1, wherein the fluid gel comprising particles formed from gellan and divalent cations is present both before and after thermal treatment. 3. A heat-treated beverage according to any one of clauses 1 to 3, wherein the amount of gellan in the beverage is 0.05 to 0.5% by weight, preferably 0.05 to 0.11% by weight, based on the total weight of the beverage. 4. The heat-treated beverage of any one of clauses 1 to 3, wherein the gellan in the fluid gel is low acyl gellan. 5. The heat-treated beverage according to any one of clauses 1 to 4, wherein the particles formed from gellan and divalent cations in the fluid gel have a particle size of 10 to 1000 μm, for example 20 to 500 μm, preferably 30 to 100 μm. 6. The thermally processed beverage of clause 5, wherein the particle size is a d10 to d90 value based on volume. 7. A thermally treated beverage according to any one of clauses 1 to 6, wherein the beverage has a pH of at least 4, preferably between 4 and 7. 8. The heat-treated beverage of any one of clauses 1 to 7, wherein the beverage has a viscosity in the range of 100 to 15,000 mPa.s, for example 1,000 to 10,000 mPa.s, measured at a shear rate of 0.1 1 / s. 9. The heat-treated beverage of any one of clauses 1 to 8, wherein the beverage has a viscosity in the range of 1 to 1000 mPa.s, such as 10 to 1000 mPa.s, measured at a shear rate of 100 1 / s. 10. A thermally treated beverage according to any one of clauses 1 to 9, wherein the beverage has a Φτ of 4 to 75 Pa, preferably 20 to 60 Pa, when measured according to the BRUCE protocol in the Examples. 11. The heat-treated beverage of any one of clauses 1 to 10, wherein the fluid gel particles consist solely of gellan and the divalent cations. 12. The heat-treated beverage of any one of clauses 1 to 11, wherein the fluid gel particles do not contain any other gelling agent different from gellan. 13. The thermally treated beverage of any one of clauses 1 to 12, wherein the divalent cation is a divalent metal cation. 14. The divalent metal cation is selected from calcium, magnesium, zinc, or a mixture thereof, and preferably, the divalent metal cation is calcium (Ca 2+ 14. The thermally treated beverage according to clause 13, wherein 15. A method for producing a thermally processed beverage comprising a fluid gel, comprising: providing a heated beverage mix comprising gellan, divalent cations, and an aqueous liquid, the beverage mix comprising 0.001 to 0.1 wt. % divalent cations based on the total weight of the beverage; cooling the heated beverage mixture under shear to form a cooled beverage comprising a fluid gel including particles formed from the gellan and the divalent cations; heat-treating the cooled beverage comprising a fluid gel to obtain a heat-treated beverage comprising a fluid gel; A method comprising: 16. The method according to clause 15, wherein the heat treatment step comprises heating the beverage mixture at a temperature of 80 to 145°C, preferably 100 to 140°C, even more preferably 120 to 140°C. 17. The method according to clause 15 or 16, wherein the shearing is carried out at a shear rate of 400 to 10,000 rpm, preferably 1000 to 2000 rpm, or 4000 to 8000 rpm. 18. A thermally processed beverage comprising a fluid gel obtained by the method of any one of clauses 15 to 17. [Example]

[0124] In the following examples, all calcium concentrations are expressed as 1M calcium chloride concentrations.

[0125] Methods and Materials The methods and materials used in the examples are described below.

[0126] material The gellan used in the examples was Kelcogel F from CPKelco. The water used in the examples was demineralized water or milliQ water. The CaCl2·2H2O used in the examples was obtained from Dr Paul Lohmann. The alginate used in the examples was Alginate Vivapur FD120 from JRS.

[0127] shearing device The shear devices used to produce the fluid gels in the examples were either Silverson or Mondomix, as detailed below.

[0128] Silverson For the "Silverson" method, a laboratory mixer, Silverson L5M-A, was used with the following shear head: Emulsor screen (circle head) Slotted Disintegrating Head (Line Head)

[0129] The mixer had a double-jacketed glass reactor with a volume of 400 mL.

[0130] Hot (70°C) samples corresponding to the relevant examples were transferred from Iso blue cap bottles to double-jacketed glass reactors, the temperature of which was set to 15°C by connecting to a water bath.

[0131] Immediately after sample transfer, the shear head of the Silverson mixer was lowered into the glass reactor at a fixed height to allow for immediate stirring after sample addition.

[0132] The temperature was first reduced from 70° C. to 60° C. by pouring 200 mL of sample into a glass reactor, so that the sample temperature was 60° C. when stirring was started.

[0133] The temperature of the double-jacketed glass vessel was controlled, allowing for the cooling rate to be controlled. The cooling rate was recorded using a digital thermometer. The position of the thermometer probe in the sample remained fixed.

[0134] Stirring was continued at a speed of 4000-6000 rpm until the temperature reached 21-22°C (the minimum temperature that could be obtained in a double-jacketed vessel at 15°C within a reasonable time).

[0135] Finally, the samples were returned to the Iso blue cap bottles for storage and further analysis. The system settings remained fixed to ensure a higher level of reproducibility.

[0136] Mondomix pin agitator For the "Mondomix" method, hydration of the gelling agent was carried out at 85°C using an Ystraal mixer X50, which stirred the aqueous fluid and the relevant sample containing the gelling agent at 1200 rpm.

[0137] After hydration (typically about 5 minutes under heated conditions), calcium chloride (1 M) solution was added and the mixture was pumped through silicone tubing into a Mondomix UA-05 pin mixer. The Mondomix is ​​equipped with an axial mixing head consisting of a rotor and a stator, both of which are fitted with pins. The rotor and stator interlock as they rotate, providing constant shear. The liquids are mixed under controlled pressure to produce a homogeneous mass. The peristaltic pump was maintained at maximum capacity during production. Silicone tubing was used to connect the units of the setup.

[0138] The temperature of the sample was maintained above the gel point until it reached the pin stirrer using an isolation coat placed on the silicone tubing that conducted the fluid from the sample bottle to the pin stirrer via a peristaltic pump.

[0139] Shear (rpm) was manually controlled on the pin agitator control panel between 1000 and 2000 rpm.

[0140] The outlet temperature (T out ) was 17 to 20 degrees Celsius.

[0141] A sample of the fluid gel produced was collected in a bottle after exiting the pin stirring head.

[0142] Rheological measurements To compare the viscosity of the fluid gels, an Anton Paar rheometer, MCR series, equipped with a CC27 sanding geometry was used. The applied shear rates ranged from 0.01 to 300 s. -1 The temperature is recorded at 10 points per decade at 20°C.

[0143] Φτ Yield stress equivalent The Φτ values ​​for the following compositions are measured using a method developed by the inventors (called the BRUCE method). This method provides a measure of the ability of a fluid gel to support particles. τ refers to the yield stress and φ refers to the (area) packing fraction. Φτ values ​​can be easily obtained by performing the following method:

[0144] The BRUCE method can measure the shear yield stress of liquid / fluid gels, as defined herein, particularly of liquid / fluid gel constituent particles. For this purpose, a hard metal disk with a diameter of 20 mm and a thickness of 2 mm is attached to the end of a metal rod. A beaker containing the liquid sample to be measured is prepared. The hard metal disk is circular and is attached at a 90° angle to the end of the metal rod with the center of the hard metal disk. The hard metal disk is preferably made of any suitable metal, such as iron or steel (e.g., V2A or V4A). The beaker is sized to provide at least 1.5 cm of space around the disk to avoid any edge effects.

[0145] The rod and disc are suspended from a balance (Mettler Toledo, Model XP404S) into a beaker.

[0146] The beaker containing the liquid sample is then lifted upward at a "known rate" using a lifter / transporter (Standa, Model SM11981&143753), the probe passes through the liquid, and the net weight versus height is measured on a balance. The "test speed" / penetration speed is set slow enough so that the force required for penetration is independent of speed and viscous effects can be neglected.

[0147] A "preset speed" is identified a priori by lifting a beaker containing a liquid sample upward several times (e.g., 2-10 times) over a range of different "test speeds." At each single "test speed," the probe passes through the liquid sample and the balance measures the net weight-to-height value. In particular, at (excessively) high speeds, the net weight-to-height value increases proportionally with speed due to viscous effects. However, because viscous effects are, by definition, inherently speed-dependent, if a sufficiently slow speed is selected, the penetration force (weight) becomes independent of speed. Such a sufficiently slow speed can then be identified from tests using a single "test speed" at which the penetration force (weight) reaches a "steady-state" or "quasi-steady-state" value over time (see, e.g., force (weight) at approximately 250-300 seconds in Figure 7A, or force (weight) at approximately 220-250 seconds in Figure 7B). This sufficiently slow speed is then considered a threshold maximum value in the BRUCE measurement and represents the "preset speed" for purposes of this invention. This velocity is believed to be independent of viscous effects. The "preset velocity" can then be used to measure the amount of force (weight) at the "steady state" or "quasi-steady state" value of the liquid sample being measured.

[0148] A correction must be made for surface tension and Archimedes forces acting on the disk and adding to the yield stress force (weight) in grams. This allows the Archimedes force to be minimized relative to the yield stress contribution by controlling the thickness of the disk. The correction is expressed as a quantity of force (weight).

[0149] Such correction values ​​can be determined by repeating the same experiment as above at the "preset rate," but using a control liquid. Such a control liquid is preferably a sample that is as chemically similar as possible to the fluid-gel system being measured, and preferably exhibits the same or similar bulk density, continuous fluid phase viscosity, and wetting / surface tension as the initially measured liquid. A suitable control in this case would be a sample containing MilliQ water, for example, if the initially measured liquid was prepared, for example, by using a selected concentration of gellan gum and MilliQ water. Alternatively, for example, an ungelled pore fluid (in MilliQ water) could be used. As mentioned above, the penetration force (weight) is measured over time at "steady-state" or "quasi-steady-state" values ​​of the control liquid, and serves as a baseline measurement; this baseline measurement can be used to correct the penetration force (weight) obtained for the initially measured liquid. Correction then simply requires subtracting the baseline measurement from the penetration force (weight) of the system of interest. If the measurement of the liquid being measured results in a penetration force (weight) value of, for example, -1.2g and the baseline measurement using the control results in a penetration force (weight) value of, for example, -0.4g, the correction value is -(1.2g-0.4g), which is -0.8g.

[0150] As the disk pushes through the fixed layer of settled fluid gel particles, the measured (corrected) penetration force (weight) can then be related to the compressive yield stress of the settled fluid gel particles. In this regard, when the yield stress is applied uniformly across the disk, = πr 2 Calculate the φτ value (Phi.tau) as φτ versus the net force on the disk (measured weight difference of 0.8 g in this example). Φτ (Phi.tau) is a convolution of the bulk yield stress of the gelling particles and the fraction of the surface area occupied by the gel particles.

[0151] This method provides a measure of the true yield stress of the gel material that forms the microgel particles, in contrast to shear rheometry, which measures the shear stress acting between gel particles.

[0152] As a pure example, we determine φτ (φτ) for water for illustrative purposes: Consider the following: R d =0.01m R r =0.001m d=0.001m Rf=1000kg / m 3 g=9.8m / s 2 σ=0.073kg / s 2

[0153] where Rd is the diameter of the disc, Rr is the radius of the rod supporting the disc, d is the thickness of the disc, Rf is the "rho-fluid", i.e., the fluid density of the sample being tested, g is the acceleration of gravity, and s is the "sigma", i.e., the surface tension of the test fluid in air; The following apply: V=πr d 2 d+πr r 2 h=3.14×10 -7 +3.14×10 -6 h

number

number

[0154] The BRUCE method is preferably carried out at 20° C. Thus, φτ (phi.tau or PhiTau) values ​​as defined herein are measured at 20° C. unless otherwise defined.

[0155] As an alternative to the corrections cited above, one can consider subtracting the Φτ value measured for the reference fluid from the Φτ value measured for the test fluid, thereby making it possible to eliminate the need to know the surface tension (s) and density (Rf) values ​​of the fluid.

[0156] Microscopic observation Particle size The samples to be measured were prepared as follows: to a 15 mL Falcon tube, add 9 mL of Milli-Q water, 0.5 mL of fluid gel sample, and 150 μL of toluidine blue 1%.

[0157] Six to nine images were taken using an Axioplan microscope, and images contained 2 to 40 particles depending on particle size and magnification.

[0158] The maximum dimension of 2-5 particles in the image is measured visually using a scale bar and the average is calculated. If the image contains at least 5 particles, the maximum dimension is measured for 5 particles; if the image contains 2-4 particles, the maximum dimension is measured for all particles in the image.

[0159] Heat Treatment The fluid gels were subjected to various heat treatments to test their stability according to the following protocol. Pasteurize at 90°C for 30 seconds Direct steam UHT at 140°C for 5 seconds Indirect UHT at 140°C for 5 seconds Pasteurization and UHT treatments were carried out using a HT320 series UHT / HTST pilot OMVE "sterilizer in-line UHT / pasteurizer" or a HT122 benchtop OMVE "sterilizer in-line UHT / pasteurizer".

[0160] Example 1 Preparation of a fluid gel The fluid gels used in the examples were prepared using the following protocol: Aqueous gellan solutions were heated to 70-80°C. The amount of gellan varied from 0.0375 wt% to 1 wt% based on the total weight of the solution depending on the heating experiment of the gellan solution.

[0161] A 1 M solution of CaCl2.2H2O was added to the gellan solution at 70-80 °C. The amount of calcium-containing solution was varied depending on the experiment.

[0162] The resulting mixture was cooled under shear. The device used to apply the shear varies depending on the experiment.

[0163] Example 2 Shearing Method The effect of shear rate and shear method was tested in which the amount of gellan was 0.1 wt % and 0.05 wt % calcium chloride (1M) was used.

[0164] Six different shear heads were tested using the Silverson shear method described above.

[0165] The Φτ values ​​for each different shear head were measured using the BRUCE method outlined above. The results of the BRUCE test are shown in Figure 1A. In Figure 1A, S1 refers to the head labeled "1," and S2 is labeled "2." In Figure 1B, the head labeled "0" is a paddle, and the BRUCE test results for this shear head are the left-most bar on the chart in Figure 1A. The results show the effect of the paddle and different Silverson heads on the yield stress of fluid gel particles.

[0166] The particle size for each different shear head was measured as outlined above, and the results are shown in Figure 1B. The results show that smaller shear heads resulted in less thick, harder particles.

[0167] Example 3 Calcium content test In this study, hydrocolloid concentrations were chosen to remain liquid-like and acceptable for drinking. As a result, the following concentrations were used: 0.1% by weight of gellan based on the total weight of the composition 0.25% by weight of alginate based on the total weight of the composition

[0168] The effect of varying the amount of calcium was studied. A series of fluid gels were prepared containing the above amounts of gelling agent (gellan or alginate) and varying amounts of calcium. The fluid gels were prepared using the Silverson method outlined above and shear head 5 of Example 1.

[0169] Bruce measurements were performed on each composition as described above. The results are shown in Figure 2. The results show that low Ca concentrations have very low Φτ values ​​and higher viscosities, which are believed to be due to less cross-linking. Higher Ca concentrations result in lower Φτ and viscosities, which are believed to be due to lower cross-linking efficiency and saturation of binding sites.

[0170] These measurements indicate an intermediate range of calcium concentration with optimal properties, which is believed to provide a good balance between calcium and gellan, resulting in optimal cross-linking of the network.

[0171] In general, gellan has a much higher Φτ than alginate, suggesting that gellan is more efficient than alginate at forming fluid gels.

[0172] Example 4 pH Test In this study, hydrocolloid concentrations were chosen to remain liquid-like and acceptable for drinking. As a result, the following concentrations were used:

[0173] For a gellan-based example, 0.1 wt % gellan with 0.05 wt % calcium chloride (1 M) based on the total weight of the composition.

[0174] For the alginate, 0.25 wt. % alginate containing 0.07 wt. % calcium chloride (1 M) based on the total weight of the composition.

[0175] The fluid gel was prepared using the Silverson method outlined above and shear head 5 of Example 1.

[0176] The effect of changing pH on fluid gel properties was tested. The pH of the samples was adjusted using HCl or NaOH (1M) to obtain samples of each gelling agent at pH 3, pH 4, and pH 7. The pH was measured using a pH probe at 20°C. Specifically, a pH meter from VWR, model number pH110, was used. The pH probe has an epoxy gel electrode and can measure pH and temperature.

[0177] Bruce measurements were performed on each composition as described above, and the results are shown in Figure 3.

[0178] The Φτ values ​​of gellan-containing fluid gels do not change significantly from pH 4 to pH 7. Below pH 4, gellan fluid gels have much lower Φτ values. For alginate, the Φτ values ​​do not change significantly from pH 3 to pH 4, then increase from pH 4 to pH 7.

[0179] It is theorized that optimal Ca binding occurs when the carboxyl groups are deprotonated, i.e., when pH > pKa. Zeta potential measurements have estimated pKa values ​​of approximately 3-3.5 for gellan and approximately 4 for alginate.

[0180] Example 5 Heat Treatment Test In this study, hydrocolloid concentrations were chosen to remain liquid-like and acceptable for drinking. As a result, the following concentrations were used: For a gellan-based example, 0.1% by weight gellan with 0.05% by weight calcium chloride (1M) based on the total weight of the composition. For alginate, 0.25% by weight of alginate containing 0.07% by weight of calcium chloride (1M) based on the total weight of the composition The effect of different heat treatments on these fluid gels was tested. Fluid gels were prepared at the pH of the gelling agent in water: pH 5.5 for gellan and pH 6.5 for alginate.

[0181] In some heat-treatment experiments, fluid gels were prepared using the Mondomix method at shear rates of 1000–2000 ppm and cooled to 17–20 °C.

[0182] For other heat treatment experiments, fluid gels were prepared using the Silverson method as described above, using head 5 from Example 1.

[0183] In the first set of heat treatment experiments, samples of each of the fluid gels (gellan and alginate) produced using the Mondomix protocol above were subjected to pasteurization as outlined above. The viscosity and Φτ of the fluid gels were measured before and after pasteurization. The results are shown in Figures 4 and 5, respectively.

[0184] In a second set of heat treatment experiments, samples of each of the fluid gels (gellan and alginate) produced using the Mondomix protocol above were subjected to direct UHT treatment as outlined above. The viscosity and Φτ of the fluid gels were measured before and after UHT treatment. The results are shown in Figures 6 and 7, respectively.

[0185] The results show that gellan fluid gels retained their physical properties, i.e., their yield stress, viscosity, and suspension properties, whereas alginate fluid gels retained their physical properties after pasteurization but not after UHT. This was observed for different concentrations.

[0186] Similar thermal stability was observed for gellan fluid gels of various concentrations prepared using the Mondomix method and heat-treated under the pasteurization protocol described above. The results are shown in Figure 4A.

[0187] Gellan fluid gels were also tested under DSC in mixtures prepared using 0.5 wt% gellan and 0.1 wt% calcium chloride (1M). The results in Figure 8 show that the gellan fluid gel has a melting point of approximately 137°C.

[0188] Additionally, microscopic images of gellan fluid gels before and after pasteurization and UHT treatment were also recorded. These are shown in Figure 9. Figure 9, 9A, is pasteurized, and Figure 9, 9B, is UHT treated. These images show no visual differences before and after pasteurization. While some visual differences are observed for UHT treatment, the fluid gel properties, such as the ability to suspend particles, e.g., contained solids, and flow under high shear, are maintained after UHT treatment. That is, after UHT treatment, the gellan fluid gels of the present invention retain their important functional properties.

[0189] For UHT treatment, gellan fluid gels were prepared using the Silverson method described above. For pasteurization treatment, gellan fluid gels were prepared using the Mondomix method described above.

[0190] In the case of pasteurization, there is no change before and after heating. In the case of UHT treatment, there is a small change in shape, which is thought to be the result of partial melting of the particles.

[0191] It is believed that the optimized fluid gel parameters of the present invention (such as gellan amount, calcium amount, pH, particle size, etc.) provide optimal gel strength. This is demonstrated in Φτ(BRUCE) measurements. Without being bound by theory, it is believed that the gels of the present invention provide the most efficient packing of gellan chains, which may explain the surprising and unexpected thermal stability of the claimed gellan fluid gels. Importantly, the gellan fluid gels of the present invention are stable enough to withstand UHT heat treatment conditions and maintain most of their gellan structure.

[0192] The thermal stability of gellan fluid gels was tested using "low" (0.01 wt%) and "high" (0.3 wt%) 1 M CaCl solutions. Fluid gels were prepared using the Mondomix method as described above, and both samples were heat-treated by direct UHT treatment.

[0193] The viscosity of "low" and "high" calcium content gellan fluid gels was measured before and after heat treatment, and the results are shown in Figure 6.

[0194] The shape of the fluid gel differs significantly between different amounts of calcium. At "low" calcium, a worm-like conformation is observed. At "high" calcium, much smaller particles are seen. These results are shown in Figure 16.

[0195] Example 6 Sensory Test Sensory testing was carried out using gellan fluid gel in water at various concentrations. Various fluid gels were prepared as follows: 0.05% by weight gellan and 0.025% by weight CaCl 0.1% by weight gellan and 0.05% by weight CaCl 0.2% by weight gellan and 0.1% by weight CaCl 0.4% by weight xanthan gum solution - prepared by hydrating xanthan in hot water followed by cooling Broken gel - composed of 0.1 wt. % gellan and 0.05 wt. % calcium chloride (1M) based on the total weight of the composition, formed by breaking a gel produced under static conditions.

[0196] Gellan fluid gels were prepared using the Silverson method and shear head 5 from Example 1 above. Gellan fluid gels were compared to xanthan gels and broken gels.

[0197] The different samples were tested by a panel of at least eight tasters, who were asked to score the thickness of the samples compared to water on a scale of 1 to 5: 0=non-existence 1 = very slight 2=Slight 3=moderate 4=Strong 5=Very strong The results are shown in Figure 10.

[0198] The gellan fluid gel was perceived in the mouth as thicker than water, but less thick than a 0.4% xanthan gum solution, which provided similar suspending properties. No particles were perceived in the mouth. The thickness in the mouth was expected and acceptable from an organoleptic standpoint.

[0199] Example 7 Application in Milk Fluid gels of the present invention, capable of suspending particles, were made directly with milk, both with and without the addition of additional calcium ions.

[0200] Various fluid gels were prepared in semi-skimmed milk containing 2.5% fat using 0.1% or 0.05% gellan by weight and optionally an additional 0.05% calcium chloride (1M). The fluid gels were prepared using the Mondomix method described above.

[0201] The viscosity of the fluid gel was measured both before and after UHT treatment, and the results are shown in Figures 11 and 12.

[0202] The results show that a lower gellan concentration was required than with water. The ability of the milk-based fluid gel to suspend particles, e.g., contained solids, was retained after UHT.

[0203] The thermal stability of different milk-based fluid gels was affected differently by heat treatment. For example, a lower yield stress (Φτ) was observed for milk-based fluid gels without additional calcium after UHT. For milk-based fluid gels containing additional Ca, there was no change in Φτ(Bruce) measurements after UHT.

[0204] Preliminary sensory data with milk indicates that gellan particles cannot be felt in the mouth (homogeneous texture) and that higher viscosity and mouthfeel were observed in the fluid gel samples compared to the corresponding non-fluid gel samples.

[0205] Sensory testing was performed comparing the fluid gels prepared above with semi-skimmed milk and whole milk. The fluid gels containing semi-skimmed milk were perceived as thicker and had better mouth-coating than the whole milk samples. A similar test was also performed on a plant-based milk substitute using WUNDA brand pea protein-based milk substitute (hereafter referred to as WUNDA milk). Gellan fluid gels were prepared using the above-described WUNDA milk and compared with WUNDA milk. A similar trend was observed for the plant-based milk substitute, with gellan fluid gels containing WUNDA milk perceived as thicker and had better mouth-coating than WUNDA milk alone. The results are shown in Figure 17.

[0206] Example 8 Shelf life test A time course study of the stability of gellan-containing fluid gels was conducted to examine their potential shelf life. Two different gellan fluid gels were prepared in milk with and without additional calcium, as follows: R1: 0.05% gellan R2: 0.05% gellan + 0.025% calcium chloride (1M)

[0207] Fluid gels were made using the Mondomix method described above and heat treated using the direct UHT method. The gels were tested for viscosity both before and after UHT heat treatment (performed as outlined above). The gels were then tested at various time points after storage at 4°C. The results are shown in the table below and in Figure 14.

[0208] [Table 1]

[0209] Example 9 Comparative UHT Treatment Test This study focuses on the different properties of fluid gels processed under UHT conditions and the corresponding non-fluid gel solutions processed under UHT conditions. The following formulation was prepared:

[0210] [Table 2]

[0211] For R1, the solution was processed to form a fluid gel. Specifically, fluid gel R1 was prepared using the Mondomix method described above, followed by UHT treatment. The UHT treatment was carried out using the direct UHT method disclosed above. After UHT treatment, sample R1 was cooled to room temperature.

[0212] For R2 and R3, the solutions were not pretreated to form a fluid gel prior to UHT treatment. Specifically, the relevant samples containing aqueous fluid and gelling agent were agitated using an Ystraal mixer X50 at 1200 rpm to obtain mixtures of hydrated gelling agent in water (R2) or milk (R3) at 85°C.

[0213] After hydration (typically about 5 minutes under heated conditions), calcium chloride (1 M) solution was added to the mixture in R2 (but not R3).

[0214] The resulting mixture is then UHT treated using the direct UHT method as disclosed above. After UHT treatment, samples R2 and R3 were cooled to room temperature.

[0215] The preformed fluid gels exhibit very different Φτ values ​​than the samples freshly processed under UHT (see 15B in Figure 15). The viscosities are comparable (see 15A in Figure 15). In the mouth, the R2 and R3 samples were very grainy compared to the preformed fluid gels prepared by Mondomix.

[0216] Viscosity profiles before and after UHT treatment of fluid gels produced in Mondomix (R1, black) compared to fluid gels produced in-situ in a UHT line by shearing with cooling in water (R2, grey) or milk (R3, black).

[0217] Although the invention has been described by example, it should be understood that variations and modifications can be made without departing from the scope of the invention as defined in the claims.

Claims

1. 1. A thermally processed beverage comprising a fluid gel comprising particles formed from gellan and divalent cations, wherein the divalent cations are present at 0.001 to 0.1 wt. % based on the total weight of the beverage.

2. 10. The thermally treated beverage of claim 1, wherein the fluid gel comprising gellan and particles formed from the divalent cations is present both before and after thermal treatment.

3. 3. A heat-treated beverage according to claim 1 or 2, wherein the amount of gellan in the beverage is 0.05 to 0.5% by weight, preferably 0.05 to 0.11% by weight, based on the total weight of the beverage.

4. 4. The thermally treated beverage according to any one of claims 1 to 3, wherein the particles formed from gellan and divalent cations in the fluid gel have a particle size of 10 to 1000 μm, for example 20 to 500 μm, preferably 30 to 100 μm.

5. A thermally treated beverage according to any one of claims 1 to 4, wherein the beverage has a pH of at least 4, preferably between 4 and 7.

6. 6. A heat-treated beverage according to any one of the preceding claims, wherein the beverage has a viscosity in the range of 100 to 15,000 mPa.s, for example 1,000 to 10,000 mPa.s, measured at a shear rate of 0.1 1 / s.

7. 7. A heat-treated beverage according to any one of the preceding claims, wherein the beverage has a viscosity in the range of 1 to 1000 mPa.s, such as 10 to 1000 mPa.s, measured at a shear rate of 100 1 / s.

8. 8. A thermally treated beverage according to any one of claims 1 to 7, wherein the beverage has a Φτ of 4 to 75 Pa, preferably 20 to 60 Pa, when measured according to the BRUCE protocol in the examples.

9. 9. A thermally processed beverage according to any one of claims 1 to 8, wherein the fluid gel particles consist solely of gellan and the divalent cations.

10. A thermally treated beverage according to any one of claims 1 to 9, wherein the divalent cation is a divalent metal cation.

11. The divalent metal cation is selected from calcium, magnesium, zinc, or a mixture thereof, and preferably, the divalent metal cation is calcium (Ca ２＋ 11. The thermally treated beverage of claim 10, wherein

12. 1. A method for producing a thermally processed beverage comprising a fluid gel, comprising: providing a heated beverage mix comprising gellan, divalent cations, and an aqueous liquid, said beverage mix comprising 0.001 to 0.1 wt. % divalent cations based on the total weight of said beverage; cooling the heated beverage mixture under shear to form a cooled beverage comprising a fluid gel including particles formed from the gellan and the divalent cations; - heat treating the cooled beverage comprising a fluid gel to obtain a heat treated beverage comprising a fluid gel; A method comprising:

13. 13. The method of claim 12, wherein the heat treatment step comprises heating the beverage mixture at a temperature of 80 to 145°C, preferably 100 to 140°C, even more preferably 120 to 140°C.

14. 14. The method according to claim 12 or 13, wherein the shearing is carried out at a shear rate of 400 to 10,000 rpm, preferably 1000 to 2000 rpm, or 4000 to 8000 rpm.

15. A thermally processed beverage comprising a fluid gel obtainable by the method of any one of claims 12 to 14.

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