CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, BEVERAGE COMPRISING THE SOLUTION, METHOD FOR INCREASING THE VOLUME, VOLUMETRIC STABILITY, FOAMING CAPACITY, FOAM EXPANSION, AND / OR FOAM DENSITY OF A FOAM PRODUCED BY AN AQUEOUS SOLUTION AND BEVERAGE PRODUCTS
By using bubble modifiers like caffeic acid esters in steviol glycosides, the bubble size and stability issues in carbonated beverages are addressed, enhancing sensory properties through smaller bubbles and more stable foam.
Patent Information
- Application Number
- BR112021020018
- Authority / Receiving Office
- BR · BR
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-04-10
- Filing Date
- 2020-04-06
- Publication Date
- 2026-07-28
- Estimated Expiration
- 2040-04-06
AI Technical Summary
Existing carbonated beverages struggle with bubble size distribution and stability, affecting sensory properties such as visual appeal and mouthfeel, as consumers prefer smaller bubbles for enhanced effervescence and foam stability.
Incorporating bubble modifiers, such as caffeic acid esters and quinic acid derivatives, into carbonated beverages to reduce bubble size and stabilize foam, using steviol glycosides to enhance sensory properties.
The solution effectively reduces bubble size and stabilizes foam, improving the visual appeal and mouthfeel of carbonated beverages, aligning with consumer preferences for smaller bubbles and thicker foam.
Smart Images

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Abstract
Description
1 / 62 CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, BEVERAGE COMPRISING THE SOLUTION, METHOD FOR INCREASING THE VOLUME, VOLUMETRIC STABILITY, FOAMING CAPACITY, FOAM EXPANSION, AND / OR FOAM DENSITY OF A FOAM PRODUCED BY AN AQUEOUS SOLUTION AND BEVERAGE PRODUCTS. REFERENCE TO RELATED APPLICATIONS.
[001] This application claims the benefit of: U.S. application No. 62 / 830,443, filed April 6, 2019, and entitled Gasified Solutions With Improved Sensory Properties; U.S. application No. 62 / 832,250, filed April 10, 2019, and entitled Gasified Solutions With Improved Sensory Properties; U.S. application No. 16 / 374,388, filed April 3, 2019, and entitled Steviol Glycoside Compositions With Reduced Surface Tension, which was published July 25, 2019, as U.S. patent application publication No. 2019 / 0223482; international application No. PCT / US2018 / 054804, filed October 8, 2018, and entitled Steviol Glycoside Compositions With Reduced Surface Tension; International application no. PCT / US2018 / 054691, filed on October 5, 2018, and entitled Steviol Glycoside Solubility Enhancers; US provisional application serial no. 62 / 569,279, filed on October 6, 2017, and entitled Steviol Glycoside Solubility Enhancers; and US provisional application serial no. 62 / 676.722, filed on May 25, 2018, and entitled Methods for Making Yerba Mate Extract Composition. The entirety of each of these applications is incorporated herein by reference. FIELD
[002] The present disclosure relates generally to carbonated solutions, for example, a carbonated beverage or a drink. Petition 870230028868, dated 05 / 04 / 2023, p. 7 / 14 / 62 nitrogenated and, more particularly, provides carbonated solutions with enhanced bubble properties. BACKGROUND
[003] Carbonated beverages are sold in very large volumes worldwide. The bubbles in such beverages can enhance the appearance, flavor release, and mouthfeel of the drink. Non-alcoholic carbonated beverages obtain their bubbles through carbonation, i.e., dissolved CO2. Factors impacting the number of bubbles likely to form in a single glass include interactions between dissolved CO2, small pockets of gas trapped in particles that act as bubble nucleation sites, and upward bubble dynamics. Alcoholic beverages can obtain bubbles through carbonation (e.g., sparkling wines) or through nitrogenation, i.e., dissolved nitrogen gas (e.g., beer). Some coffee and energy drinks are nitrogenated to enhance mouthfeel and flavor release.
[004] Bubbles generally appear in carbonated beverages when CO2 concentration levels are 3 to 5 times higher than the saturation equilibrium value and depend on pre-existing gas-liquid interfaces (Lubetkin & Blackwell, 1988; Wilt, 1986). The growth rate and upward velocity of bubbles are influenced by the concentration of carbon dioxide available in the liquid phase and by the presence of surfactant molecules (proteins, sugar) in the solution and on the bubble wall, making them slower or faster (Jones, Evans, & Galvin, 1999; Odake, 2001).
[005] The initial bubble size distribution in a beverage foam depends on the history of bubble formation, i.e., the number of bubbles per unit time, the shape and wetting properties of the cavities, the supersaturation of the liquid with gas, the rheological properties of the liquid surface, and the speed and direction of the Petition 870210111885, dated 02 / 12 / 2021, p. 8 / 91 / 62 flow of the liquid surrounding the bubble.
[006] The gaseous phase in beverages can have a considerable effect on sensory properties, including visual appeal, mouthfeel, and flavor release. Generally, the benefits of bubbles at a sensory level are threefold: 1) visual appeal of the frequency of bubble formation (Liger-Belair, 2006), 2) the rate of growth of bubbles rising in the glass (Liger-Belair et al., 2012), 3) a tingling sensation in the mouth. A head of foam in a beverage can also make it more appealing. Furthermore, the size distribution and the number of bubbles formed per unit of time affect the appearance and stability of the foam. A wide bubble size distribution can promote a sense of spiky bubbles or thick foam. Smaller bubbles contribute to a more effervescent sensation or more creamy foam. Studies by Barker et al.(2002) showed that consumers prefer smaller bubbles; in sensory studies, 87% of examiners were able to correctly identify the most highly carbonated sample and 73% of examiners perceived that the sample containing the smaller bubbles was more highly carbonated. In other related tests, samples containing smaller bubbles were consistently preferred over samples with larger, normal-sized bubbles. SUMMARY
[007] The present disclosure relates generally to carbonated aqueous solutions, for example, carbonated beverages, with bubble modifiers that improve bubble properties by reducing the bubble size in the liquid phase, which reduces the bubble size in a foam in the solution, and / or stabilizes the foam in the solution. BRIEF DESCRIPTION OF THE FIGURES
[008] Figure 1 shows digital photographs of bubbles for an aqueous solution of steviol glycoside during and after bubbling. Petition 870210111885, dated 02 / 12 / 2021, page 9 / 91 / 62 (spraying) with air for 40 seconds.
[009] Figure 2A shows digital photographs of bubbles for an aqueous solution of steviol glycoside with bubble modifier after bubbling with air for 40 seconds.
[0010] Figure 2B shows digital photographs of bubbles for an aqueous solution of steviol glycoside with bubble modifier after bubbling with air for 60 seconds.
[0011] Figure 2C shows digital photographs of bubbles for an aqueous solution of steviol glycoside with bubble modifier after bubbling with air to achieve a final volume of 250 mL.
[0012] Figure 3A shows digital bubble photographs for a lemon-lime-sicilian flavored steviol glycoside solution with bubble modifier after bubbling with air for 40 seconds.
[0013] Figure 3B shows digital bubble photographs for a lemon-lime-sicilian flavored steviol glycoside solution with bubble modifier after bubbling with air for 60 seconds.
[0014] Figure 3C shows digital bubble photographs for a lemon-lime-sicilian flavored steviol glycoside solution with bubble modifier after bubbling with air to achieve a final volume of 250 mL.
[0015] Figure 4A shows digital photographs of bubbles for a kola nut flavored steviol glycoside solution with bubble modifier after bubbling with air for 40 seconds.
[0016] Figure 4B shows digital photographs of bubbles for a cola-flavored steviol glycoside solution with bubble modifier after bubbling with air for 40 seconds.
[0017] Figure 4C shows digital photographs of bubbles for a cola-flavored steviol glycoside solution with bubble modifier after bubbling with air to achieve a final volume of 250 mL. Petition 870210111885, dated 02 / 12 / 2021, page 10 / 91 / 62
[0018] Figure 5A shows digital photographs of bubbles for a steviol glycoside solution during and after bubbling with air or nitrogen gas for 40 seconds.
[0019] Figure 5B shows digital photographs of bubbles for a steviol glycoside solution with bubble modifier during and after bubbling with air or nitrogen gas for 40 seconds.
[0020] Figure 5C shows digital photographs of bubbles for a steviol glycoside solution with bubble modifier and preservatives during and after bubbling with air or nitrogen gas for 40 seconds.
[0021] Figure 6A shows digital photographs of bubbles for an orange-flavored steviol glycoside solution during and after bubbling with air or nitrogen gas for 40 seconds.
[0022] Figure 6B shows digital photographs of bubbles for an orange-flavored steviol glycoside solution with a bubble modifier during and after bubbling with air or nitrogen gas for 40 seconds.
[0023] Figure 7A is a graph reflecting the average foam bubble size over time for aqueous solutions sprayed with air.
[0024] Figure 7B is a graph reflecting the average foam bubble size over time for aqueous solutions sprayed with nitrogen.
[0025] Figure 7C is a graph that reflects the average foam bubble size over time for aqueous solutions sprayed with air and nitrogen.
[0026] Figure 7D is a graph reflecting the average foam bubble size over time for an aqueous solution with orange flavor sprayed with air and nitrogen.
[0027] Figure 8 is a photograph of carbonated water samples. Petition 870210111885, dated 02 / 12 / 2021, page 11 / 91 / 62 unsweetened with different concentrations of bubble modifiers. Detailed description
[0028] The disclosure relates generally to bubble modifiers that can 1) reduce bubble size in carbonated aqueous solutions, for example, carbonated or nitrogenated beverages, and 2) when used in conjunction with steviol glycoside compounds in modified steviol glycoside solutions, increase foam volume and foam stability. This can improve the sensory properties, for example, visual appeal and mouthfeel, of beverages incorporating features according to this disclosure.
[0029] As used in the present invention, a carbonated aqueous solution is an aqueous solution containing dissolved gas in a concentration that will cause the solution to effervesce when at rest (i.e., not actively stirred or agitated) in a smooth-walled glass container. The effervescence of a given solution may depend on several factors, such as the solution pressure and its temperature. For the purposes of this disclosure, an aqueous solution may be considered a carbonated aqueous solution if it effervesces when the solution is at 15.6 °C and under an ambient air pressure of 1 atmosphere; a temperature of 15.6 °C and an ambient air pressure of 1 atmosphere are referred to in the present invention as STP.
[0030] As used herein, a modified steviol glycoside solution is an aqueous solution containing steviol glycoside and a bubble modifier.
[0031] As the term is used in the present invention, steviol glycoside refers to the total content of steviol glycoside compounds. The weight of a steviol glycoside and its constituent steviol glycoside compounds is determined on a dry (anhydrous) basis. Except where otherwise expressed herein, an amount of steviol glycoside refers to the weight percentage (% by weight) of the total content of Petition 870210111885, dated 02 / 12 / 2021, page 12 / 91 / 62 steviol glycoside compounds.
[0032] Unless expressly stated otherwise, ppm is on a weight basis. Percentages not otherwise defined herein are weight percentages unless the context indicates otherwise.
[0033] As detailed below, solutions according to this disclosure include a bubble modifier and may also include steviol glycoside. Bubble modifier
[0034] The bubble modifiers disclosed in the present invention can reduce the size of bubbles in aerated aqueous solutions and / or modify the foaming characteristics of modified steviol glycoside solutions, for example, by modifying the foaming capacity (discussed below), the volumetric stability of the foam, the amount of foam produced, the foam expansion (discussed below), and / or the foam density. A bubble modifier may include a single bubble modifier compound or more than one bubble modifier compound.
[0035] Examples of bubble-modifying compounds suitable for use in aerated aqueous solutions and modified steviol glycoside solutions of this disclosure include: • caffeic acid; an ester of caffeic acid; an ester of caffeic acid and quinic acid; a monocaffeoylquinic acid, namely, an ester of caffeic acid and quinic acid comprising a single moiety of caffeic acid, for example, chlorogenic, cryptochlorogenic or neochlorogenic acid (the structures of each are provided in the present invention); an ester of caffeic acid and quinic acid comprising more than one moiety of caffeic acid, such as a dicaffeoylquinic acid, namely, an ester of caffeic acid and quinic acid comprising two moieties of caffeic acid, for example, Petition 870210111885, dated 02 / 12 / 2021, page 13 / 91 / 62 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid or 4,5-dicaffeoylquinic acid (the structures of each are provided in the present invention); • ferulic acid; an ester of ferulic acid; an ester of ferulic acid and quinic acid; a monoferuloylquinic acid, namely, an ester of ferulic acid and quinic acid comprising a single ferulic acid moiety, for example, 3-O-feruloylquinic acid, 4-O-feruloylquinic acid, 5-O-feruloylquinic acid; an ester of ferulic acid and quinic acid comprising more than one ferulic acid moiety, such as a diferuloylquinic acid, namely, an ester of ferulic acid and quinic acid comprising two ferulic acid moieties, for example, 3,4-diferuloylquinic acid, 3,5-diferuloylquinic acid and 4,5-diferuloylquinic acid; • quinic acid, an ester of quinic acid; • tartaric acid, a tartaric acid derivative, an ester of tartaric acid, an ester of a tartaric acid derivative; • 3-(3,4-dihydroxyphenyl)lactic acid, a derivative of 3-(3,4-dihydroxyphenyl)lactic acid, an ester of 3-(3,4-dihydroxyphenyl)lactic acid, an ester of a derivative of 3-(3,4-dihydroxyphenyl)lactic acid; • p-coumaric acid, an ester of p-coumaric acid, an ester of p-coumaric acid and quinic acid, an ester of p-coumaric acid and quinic acid comprising a single portion of p-coumaric acid, an ester of p-coumaric acid and quinic acid comprising more than one portion of p-coumaric acid; and • sinapic acid, an ester of sinapic acid, an ester of sinapic acid and quinic acid, an ester of sinapic acid and quinic acid comprising a single portion of sinapic acid, an ester of sinapic acid and quinic acid comprising more than one portion of sinapic acid.
[0036] These bubble-modifying compounds may be in your Petition 870210111885, dated 02 / 12 / 2021, p. 14 / 91 / 62 acidic form or in a salt form, for example, as a quaternary ammonium, sodium, potassium, lithium, magnesium or calcium salt, or a combination of these salts.
[0037] In some respects, the bubble modifier comprises at least one, at least two, at least three, or more compounds selected from the group consisting of 3-O-coumaroylquinic acid, 4-O-coumaroylquinic acid, 5-O-coumaroylquinic acid, 3,4-dicumaroylquinic acid, 3,5-dicumaroylquinic acid and 4,5-dicumaroylquinic acid.
[0038] Caffeic acid has the following structure: O / OH HO ' . Ferulic acid has the following structure: p-Coumaric acid has the following structure: Sinapic acid has the following structure: Quinic acid has the following structure: Petition 870210111885, dated 02 / 12 / 2021, p. 15 / 91 / 62hOçO2H HO' S^OH ÕH . 3-(3,4-dihydroxyphenyl)lactic acid has the following structure: and can be in D and L forms.
[0039] Examples of esters of the various acids contemplated in the present invention include the caffeic acid and tartaric acid ester, which includes chicoric acid having the structure: which has two molecules of caffeic acid bonded to a core of tartaric acid; and caftaric acid which has the structure: Petition 870210111885, dated 02 / 12 / 2021, p. 16 / 91 11 / 62 which has a caffeic acid molecule bonded to a tartaric acid core.
[0040] Examples of esters of the various acids contemplated in the present invention also include the ester of caffeic acid and 3-(3,4-dihydroxyphenyl)lactic acid, including, for example, rosmarinic acid, which has the structure:
[0041] Examples of esters of the various acids contemplated in the present invention include caffeic acid and quinic acid esters, which include monocaffeoylquinic acids (e.g., chlorogenic acid, neochlorogenic acid, and cryptochlorogenic acid), and dicaffeoylquinic acids (e.g., 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, and 4,5-dicaffeoylquinic acid), as well as salts of these substances: Petition 870210111885, dated 02 / 12 / 2021, page 17 / 91 / 62 Neochlorogenic acid THE Cryptochlorogenic acid Petition 870210111885, dated 02 / 12 / 2021, page 18 / 91 / 62 1,3-dicaffeoylquinic acid Petition 870210111885, dated 02 / 12 / 2021, page 19 / 91 / 62 4,5-dicaffeoylquinic acid 3,5-dicaffeoylquinic acid 3,4-dicaffeoylquinic acid, along with 4,5-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, and 3,4-dicaffeoylquinic acid, are the most predominant in the compositions contemplated in the present invention and are abundantly present in stevia, yerba mate, globe artichoke, and green coffee.
[0042] Caffeic acid, monocaffeoylquinic acids, dicaffeoylquinic acids and other bubble-modifying compounds may be Petition 870210111885, dated 02 / 12 / 2021, page 20 / 91 / 62 considered weak acids and each may exist in at least one of their conjugate acid forms, conjugate base forms (e.g., in their salt form), and conjugate base form with mixed conjugate acid, wherein a fraction (e.g., molar fraction) of the compounds exists in the conjugate acid form and another fraction exists in the conjugate base form. The ratio of conjugate acid form to conjugate base form for caffeic acid, monocaffeoylquinic acids, dicaffeoylquinic acids, and other bubble-modifying compounds will depend on several factors, including the pKa of each compound and the pH of the composition.
[0043] Examples of caffeic acid salts, monocaffeoylquinic acids, dicaffeoylquinic acids and other bubble-modifying compounds include, but are not limited to, their quaternary ammonium, sodium, potassium, lithium, magnesium and calcium salts, or a combination of these salts.
[0044] In some respects, the bubble modifier may be enriched with one or more of caffeic acid, monocaffeoylquinic acids, and dicaffeoylquinic acids. The term enriched refers to an increase in the amount of one of caffeic acid, monocaffeoylquinic acids, and dicaffeoylquinic acids relative to one or more other compounds present in the bubble modifier. A bubble modifier that is enriched with one or more of caffeic acid, monocaffeoylquinic acids, and dicaffeoylquinic acids may improve bubble modification, for example, by further reducing bubble size in a gaseous aqueous solution and / or modifying the foam properties of a modified steviol glycoside solution.
[0045] In some respects, a bubble modifier enriched with one or more dicaffeoylquinic acids may comprise 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 60% or more, 70% or more, 80% or more Petition 870210111885, dated 02 / 12 / 2021, page 21 / 91 / 62 more, or 90% or more dicaffeoylquinic acids. In other respects, a bubble modifier that is enriched with dicaffeoylquinic acids may comprise 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 60% or more, 70% or more, or 80%. or more, or 90% or more of a combination of one or more of 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid and 4,5-dicaffeoylquinic acid, and salts thereof.
[0046] Certain preferred bubble modifiers specifically include a dicaffeoylquinic (DCQ) component and a monocaffeoylquinic (MCQ) component. The DCQ component includes at least one, desirably at least two or at least three, dicaffeoylquinic acids or their salts. In one aspect, the DCQ component includes at least one compound selected from the group consisting of 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid, and salts thereof. The MCQ component includes at least one, desirably at least two or at least three, monocaffeoylquinic acids or their salts. In one aspect, the MCQ component includes at least one compound selected from the group consisting of chlorogenic acid, neochlorogenic acid, cryptochlorogenic acid, and salts thereof.
[0047] The DCQ component and the MCQ component may together comprise more than 50 percent by weight (% (weight) or % by weight) of the bubble modifier. Desirably, the DCQ component and the MCQ component together comprise more than 60% (by weight), more than 70% (by weight), more than 80% (by weight), more than 90% (by weight), more than 95% (by weight) or more than 98% (by weight) of the bubble modifier.
[0048] The bubble modifier may include bubble-modifying compounds in addition to MCQ and DCQ components. A useful bubble modifier Petition 870210111885, dated 02 / 12 / 2021, p. 22 / 91 / 62 includes component MCQ, component DCQ, and one or more compounds selected from the group consisting of caffeic acid, ferulic acid, p-coumaric acid, sinapic acid, quinic acid, 3-(3,4-dihydroxyphenyl)lactic acid, tartaric acid, chicoric acid, caftaric acid, monoferuloylquinic acids, diferuloylquinic acids, monocoumaroylquinic acids, dicoumaroylquinic acids and salts thereof. In certain respects, such bubble modifier includes component MCQ, component DCQ and one or more compounds selected from the group consisting of caffeic acid, monoferuloylquinic acids, diferuloylquinic acids and salts thereof. In one implementation, the MCQ component and the DCQ component, and one or more compounds selected from that group together comprise more than 70% (by weight), more than 75% (by weight), more than 80% (by weight), more than 90% (by weight), more than 95% (by weight), or more than 98% (by weight) of the bubble modifier.
[0049] The weight ratio between the DCQ component and the MCQ component may be at least 0.2, at least 0.33, or at least 0.5. Preferably, this ratio is at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10. In certain respects, this ratio is not greater than 20 or is not greater than 10, for example, between 1 and 20, preferably between 1 and 10, between 2 and 10, between 3 and 10, between 4 and 10, or between 5 and 10. Depending on the botanical source, obtaining increasingly higher ratios between the DCQ component and the MCQ component may increase the processing cost to obtain the bubble modifier without adversely affecting a commercially relevant use, for example, in a beverage that has less than 1,000 ppm of steviol glycoside.
[0050] Certain commercially useful bubble modifiers have a weight ratio between the DCQ component and the MCQ component of between 0.33 and 5. Such compositions have been found to produce non-alcoholic beverages with Petition 870210111885, dated 02 / 12 / 2021, page 23 / 91 / 62 particularly desirable sensory properties. Thus, in some respects, the ratio between the weight of the DCQ component and the weight of the MCQ component in the bubble modifier is between 0.33 and 5, between 0.5 and 5, between 1 and 5, between 1.5 and 5, between 2 and 5, between 3 and 5, between 0.5 and 4, between 1 and 4, between 1.5 and 4, between 0.5 and 3, between 1 and 3, or between 1.5 and 3.
[0051] A suitable bubble modifier has a weight ratio between the DCQ component and the MCQ component of at least 1, preferably at least 2, at least 3, or at least 4, and the DCQ component and the MCQ component together comprise more than 70% (by weight), for example, more than 80% (by weight) or more than 90% (by weight) of the bubble modifier.
[0052] Bubble modifiers, or bubble-modifying compounds for use in bubble modifiers, can be isolated in a variety of forms. Some suitable processes are disclosed in more detail in U.S. Provisional Application Serial No. 62 / 676,722, filed May 25, 2018, and entitled Methods for Making Yerba Mate Extract Composition. For example, bubble modifiers or bubble-modifying compounds for use in bubble modifiers can be isolated from a botanical source comprising one or more of monocaffeoylquinic acid, dicaffeoylquinic acid, and salts thereof. For example, yerba mate biomass and stevia biomass can be used to prepare suitable bubble modifiers. In an exemplary process, a bubble modifier is prepared from commercially obtained fragmented yerba mate biomass.Briefly, yerba mate biomass is suspended in a 50% (v / v) ethanol / water solution, stirred for at least 1 hour, and the resulting mixture is filtered to obtain an initial extract. The initial extract is diluted to 35% (v / v) ethanol with water and refiltered. The refiltered permeate is then applied to an AMBERLITE® FPA 53 resin column that has been equilibrated to 35% (v / v) ethanol / water, and the permeate column is... Petition 870210111885, dated 02 / 12 / 2021, page 24 / 91 / 62 discarded. The column is washed with 35% (v / v) ethanol / water and the column permeate is discarded. The column is then eluted with 10% (weight by volume) FCC (Food Chemicals Codex) grade sodium chloride in 50% (volume by volume) ethanol / water and the eluent is retained. Nitrogen gas is blown at room temperature over a surface of the eluent to remove ethanol and reduce the eluent to 1 / 3 of its original volume. The reduced volume eluent is then filtered through a 0.2 μm polyethersulfone filter and then decolorized by passing through a 3 kDa molecular weight shear membrane. The decolorized permeate is retained and desalinated by passing through a nanofiltration membrane. The desalinated permeate is then freeze-dried to obtain the bubble modifier, or a composition of bubble-modifying compounds that can be used in a bubble modifier.This process is also suitable for obtaining bubble modifiers or bubble modifier compounds for use in bubble modifiers, from stevia biomass, and can be adapted for obtaining bubble modifiers or bubble modifier compounds from other botanical sources.
[0053] In some respects, the bubble modifier, or bubble modifier compounds for use in bubble modifiers, may be isolated from botanical sources. Some examples of botanical sources from which bubble modifiers or bubble-modifying compounds can be isolated include *Eucommoia ulmoides*, *Linoceros*, *Nicotiana benthamiana*, globe artichoke, cartoon, stevia, *Stevia rebaudiana*, monella fruit, coffee, coffee beans, green coffee beans, tea, white tea, yellow tea, green tea, oolong tea, black tea, red tea, post-fermented tea, bamboo, heather, sunflower, blueberries, cranberries, bilberries (genus *Vaccinium*), grouseberries (*Vaccinium scoparium*), whorleberry (genus *Vaccinium*), cranberry (*Vaccinium vitis-idaea*), cowberry, huckleberry (a species of blueberry), grapes, chicory, purple echinacea, echinacea, Eastern pellitory. Petition 870210111885, dated 02 / 12 / 2021, page. 25 / 91 / 62 of-the-wall, Lichwort, greater celandine, tetterwort, Nipplewort (Lapsana communis), swallowwort (Cynanchum L.), Canada bloodroot, common nettle, stinging nettle, potato, potato leaves, eggplant, eggplant, tomato, cherry tomato, bitter apple, trumpet vine (Datura stramonium), sweet potato, apple, peach, nectarine, cherry, wild cherry, wild cherry, apricot, almond, plum, prune, holly, yerba mate, Ilex paraguariensis, guayusa, Yaupon holly (Ilex vomitoria), kuding, guarana, cocoa powder, cocoa bean, cacao, cocoa bean, kola nut, kola nut tree, kola nut, kola tree, hornwort (Ceratophyllum demersum), fern ostrich, eastern ostrich fern (Matteuccia orientalis), fiddlehead fern, shutttlecock fern, rose fern, royal fern, bracken (genus Pteridium), Pteridium aquilinum, eagle fern, eastern bracken fern, dandelion, algae, seagrass, clove,Cinnamon, Indian bay leaf, nutmeg, bay leaf (Laurus nobilis), bay leaf, basil, great basil, St. John's wort, thyme, sage, garden sage, common sage, culinary sage, rosemary, oregano, wild marjoram, sweet marjoram, knotted marjoram, sprout marjoram, dill (Anethum graveolens), anise, star anise, fennel, Florence fennel, tarragon, mugwort, licorice, soy, soybeans, sesame, wheat, rice, canola, broccoli, cauliflower, cabbage, cauliflower, cabbage, Chinese cabbage, kale, collard greens, Brussels sprouts, kohlrabi, cascara, elderberry, assa-peixe, burdock, valerian and chamomile. In some aspects, the botanical source is yerba mate, chicory, rosemary, artichoke, cowrie shell, and / or stevia.
[0054] In some respects, the bubble modifier may be a blend of bubble-modifying compounds isolated from more than one botanical source. It may, instead, be a mixture of bubble-modifying compounds isolated from more than one botanical source and / or a synthesized or fermented hydroxycinnamic acid. Petition 870210111885, dated 02 / 12 / 2021, p. 26 / 91 / 62
[0055] Some plants can produce bubble modifiers that are enriched with one or more of the following: caffeic acid, monocaffeoylquinic acids, and dicaffeoylquinic acids. For example, bubble modifiers isolated from the yerba mate plant (Ilex paraguariensis) and some other plants are naturally enriched with dicaffeoylquinic acids.
[0056] Some compounds may adversely affect the taste or aroma of a gaseous aqueous solution or a modified steviol glycoside solution. Certain bubble modifiers, such as those prepared from a plant extract, do not include one or more of the compounds shown in Table 1, or any combination thereof, above the preferred content levels disclosed. All preferred content levels are stated as a percentage by weight based on dry weight. Certain commercially desirable solid (dry) bubble modifiers do not include more than the preferred content level of the list of compounds shown in Table 1. Table 1. Compound Class | Preferred Content Level (% by weight) | % by weight of compounds in solid (dry) bubble modifiers | Organic acids | <3%, preferably <2%, <1%, or 0% | malonate, malonic acid, oxalate, oxalic acid, lactate, lactic acid, succinate, succinic acid, malate, malic acid, citrate, citric acid | <0.5%, preferably <0.25% or 0% | tartrate, tartaric acid, pyruvate, pyruvic acid, fumarate, fumaric acid, ascorbic acid, sorbate, sorbic acid, acetate, acetic acid.Inorganic acids <1%, preferably <0.5% or 0%: sulfate, sulfuric acid, phosphate, phosphoric acid, nitrate, nitric acid, nitrite, nitrous acid, chloride, hydrochloric acid, ammonia, ammonium. Flavonoids, isoflavonoids and neoflavonoids <5%, preferably <4%, <3%, or <2%, more preferably <1%, <0.5%, or 0%: quercetin, kaempferol, myricetin, fisetin, galangin, isorhamnetin, pachipodol, rhamnazine, pyranoflavonols, furanoflavonols, luteolin, apigenin, tangeritin, taxifolin (or dihydroquercetin), dihydrokaempferol, hesperetin, naringenin, eriodictiol, homoeriodictiol, genistein, daidzein, glycitein. Glycosides Flavonoids <5%, preferably <4%, <3%, or <2%, more preferably <1%, <0.5%, or 0%: hesperidin, naringin, rutin, quercitrin, luteolin glycoside, quercetin xyloside. Anthocyanidins <5%, preferably <4%, <3%, or <2%, more preferably <1%, <0.5%, or 0%: cyanidin, delphinidin, malvidin, pelargonidin, peonidin, petunidin. Petition 870210111885, dated 02 / 12 / 2021, p. 27 / 91 / 62 Tannins <1%, preferably <0.5%, <0.25%, or 0% tannic acid. Amino acids + total protein <0.1%, preferably <0.05%, or 0% alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine. Total fat <1%, preferably <0.5%, <0.25%, or 0% monoglycerides, diglycerides, triglycerides. Monosaccharides, disaccharides, and polysaccharides <1% glucose, fructose, sucrose, galactose, ribose, trehalose, trealulose, lactose, maltose, isomaltose, isomaltulose, mannose. Tagatose, arabinose, rhamnose, xylose, dextrose, erythrose, threose, maltotriose, panose. Sugar alcohols <1%: glycerol, sorbitol, mannitol, xylitol, maltitol, lactitol, erythritol, isomalt, inositol. Dietary fiber <0.1%, preferably <0.05% or 0%: acacia gum (arabic), agar-agar, algin alginate, arabinoxylan, beta-glucan, beta-mannan, carrageenan gum.Carob or locust bean gum, fenugreek gum, galactomannans, gellan gum, glucomannan or konjac gum, guar gum, hemicellulose, inulin, karaya gum, pectin, polydextrose, plantain bark mucilage, resistant starches, tara gum, tragacanth gum, xanthan gum, cellulose, chitin and chitosan from the composition. Steviol glycoside compounds <55% etevioside; steviolbioside; rubusoside; 13- and 19SMG; dulcosides A, B, C, D; and rebaudiosides A, B, C, D, E, F, I, M, N, O, T Saponins <0.5%, preferably <0.25% or 0% glycosylated ursolic acid and glycosylated oleanolic acid Terpenes other than saponins and steviol glycoside compounds <0.5%, preferably <0.25% or 0% eugenol, geraniol, geranial, alpha-ionone, beta-ionone, epoxy-ionone, limonene, linalool, linalool oxide, nerol, damascenone Lipid oxidation products <0.5%, preferably <0.25% or 0% Decanone, decenal, nonenal, octenal, heptenal, hexenal, pentenal, pentenol, pentenone, hexenone,Hydroxynonenal, malondialdehyde. Polycyclic aromatic hydrocarbons <0.1%, preferably <0.05% or 0%. Acenaphthalene, Acenaphtylene, Anthracene, Benzo(a)anthracene, Benzo(a)pyrene, Benzo(b)fluoranthene, Benzo(k)fluoranene, Benzo(ghi)perylene, Chrysene, Dibenzo(a,h)anthracene, Fluoranene, Indeno(1,2,3-cd)pyrene, Naphthalene, Phenanthrene, Pyrene. Other compounds <0.1%, preferably <0.05% or 0%. Chlorophyll, furans, furan-containing chemicals, theobromine, theophylline and trigonelline.
[0057] A suitable bubble modifier, which may be particularly useful in gaseous aqueous solutions, includes <10% (by weight), <5% (by weight), <4% (by weight), <3% (by weight), <2% (by weight), <1% (by weight), <0.5% (by weight), <0.25% (by weight), <0.10% (by weight) or 0% (by weight) of steviol glycoside compounds. In selected implementations, such a bubble modifier is substantially free of Petition 870210111885, dated 02 / 12 / 2021, page 28 / 91 / 62 steviol glycoside compounds. Particularly when the bubble modifier is derived from stevia, for example, stevia leaves, reducing the amount of steviol glycoside compounds, or not including steviol glycoside compounds, in the bubble modifier allows for a more precise selection of steviol glycoside compounds or other sweeteners to obtain a desired flavor profile from a modified steviol glycoside solution.
[0058] As noted above, some compounds may adversely affect the taste or aroma of a gaseous aqueous solution or a modified steviol glycoside solution. A useful bubble modifier includes an MCQ component, a DCQ component, and less than 0.3% (by weight), for example, 0% malonate, malonic acid, oxalate, oxalic acid, lactate, lactic acid, succinate, succinic acid, malate, or malic acid; or less than 0.05% (by weight), for example, 0% pyruvate, pyruvic acid, fumarate, fumaric acid, tartrate, tartaric acid, sorbate, sorbic acid, acetate, or acetic acid; or less than about 0.05% (by weight), for example, 0% chlorophyll.In one aspect, the bubble modifier is free from malonate, malonic acid, oxalate, oxalic acid, lactate, lactic acid, succinate, succinic acid, malate, and malic acid; or is free from pyruvate, pyruvic acid, fumarate, fumaric acid, tartrate, tartaric acid, sorbate, sorbic acid, acetate, and acetic acid; or is free from chlorophyll. Steviol glycosides
[0059] Aqueous solutions according to disclosure aspects may include one or more steviol glycoside compounds and one or more bubble modifier compounds, as well as other compounds. Steviol glycoside compounds generally have the formula Petition 870210111885, dated 02 / 12 / 2021, page 29 / 91 24 / 62 wherein steviol (Ri and R2 = H) is the main aglycone chain and Ri and R2 can each be hydrogen or one or more sugar moieties. These sugar moieties are most commonly glucose, rhamnose, or xylitol, but steviol glycoside compounds have been reported that include fructose and deoxyglucose sugar moieties.
[0060] Exemplary steviol glycoside compounds that may be useful in the solutions described herein include one or more of the following: rebaudioside A (Reb A) (CAS # 58543-16-1), rebaudioside B (Reb B) (CAS # 58543-17-2), rebaudioside C (Reb C) (CAS # 63550-99-2), rebaudioside D (Reb D) (CAS # 63279-13-0), rebaudioside E (Reb E) (CAS # 63279-14-1), rebaudioside F (Reb F) (CAS # 438045-89-7), rebaudioside M (Reb M) (CAS # 1220616-44-3), rubusoside (CAS # 63849-39-4), dulcoside A (CAS# 64432-06-0), rebaudioside I (Reb I) (MassBank Record: FU000332), rebaudioside Q (Reb Q), rebaudioside O (Reb O), rebaudioside N (Reb N) (CAS# 1220616-46-5), 1,2-stevioside (CAS# 57817-89-7), 1,3-stevioside (Reb G), stevioside-1,2-bioside (MassBank Record: FU000299), this viol-1,3-bioside, steviol-13-0glucoside (13-SMG), steviol-19-O-glucoside (19-SMG), and compounds of steviol glycoside having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or added sugars (e.g., glucose,rhamnose and / or xylose), and isomers thereof. See, for example, Steviol Glycosides Chemical and Technical Assessment 82nd JECFA, 2016, reviewed by Jeff Moore, Food Agric. Org., Petition 870210111885, dated 02 / 12 / 2021, p. 30 / 91 / 62
[0061] Exemplary steviol glycosides may include rebaudioside M, rebaudioside D, rebaudioside A, rebaudioside B, and / or rebaudioside N. In some respects, one or more of the steviol glycoside compounds are produced by fermentation by a modified microorganism. In some respects, one or more of the steviol glycoside compounds are produced by bioconversion by an enzyme and a leaf extract. For example, rebaudioside D and M may be produced by a modified organism and then isolated to produce a steviol glycoside composition of primarily rebaudioside D and rebaudioside M as the predominant steviol glycoside compound species. In some respects, one or more of the steviol glycoside compounds are isolated from Stevia rebaudiana.
[0062] In some respects, steviol glycoside may comprise rebaudioside D and rebaudioside M in a greater amount than other steviol glycoside compounds. For example, rebaudioside M and / or rebaudioside D may be present in steviol glycoside in a total amount of about 75% (by weight) or more, about 80% (by weight) or more, preferably about 90% (by weight) or more, about 92.5% (by weight) or more, or 95% (by weight) or more, of a total amount of steviol glycoside compounds in the composition. Rebaudioside M may be the predominant steviol glycoside compound in steviol glycoside and may be present, for example, in an amount in the range of about 45% (by weight) to about 70% (by weight), about 50% (by weight) to about 65% (by weight), or about 52.5% (by weight) to about 62.5% (by weight) of the total amount of steviol glycoside compounds in the composition.Rebaudioside D may be present in a smaller quantity than rebaudioside M, such as in an amount ranging from about 25% (by weight) to about 50% (by weight), from about 30% (by weight) to about 45% (by weight), or from about 32.5% (by weight). Petition 870210111885, dated 02 / 12 / 2021, page 31 / 91 / 62 weight) to approximately 42.5% (by weight) of the total amount of steviol glycosides in the composition.
[0063] The steviol glycoside composition may optionally include smaller amounts of steviol glycoside compounds in addition to rebaudioside D and rebaudioside M. For example, the composition may include one or more of rebaudioside A, rebaudioside B, or stevioside in an amount of about 1% (by weight) or less, about 0.5% (by weight) or less, or about 0.25% (by weight) or less, of a total amount of steviol glycoside compounds in the composition. Modified steviol glycoside solutions
[0064] The amount of steviol glycoside in a modified steviol glycoside solution may vary depending on the desired use. For example, steviol glycoside may be present in a modified steviol glycoside solution at a concentration of at least 20 ppm, preferably at least 50 ppm, for example, from about 50 ppm to about 1,000 ppm, from about 50 ppm to about 10,000 ppm (1% (by weight)), from about 50 ppm to about 100,000 ppm (10% (by weight)), from about 50 ppm to about 200,000 ppm (20% (by weight)), or from about 50 ppm to about 300,000 ppm (30% (by weight)). In some aspects, steviol glycoside is present at a concentration of at least 10, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1,000 ppm.
[0065] In certain modified steviol glycoside solutions, the steviol glycoside is present at a level that can function as a flavoring, for example, as a sweetness enhancer, but below a level at which sweetness would be detectable. Such modified steviol glycoside solutions may have a steviol glycoside concentration of about 10 to 80 ppm, about 10 to 65 ppm, about 10 to 50 ppm, about 10 to 40 ppm, about 15 to 65 ppm, about 15 to 50 ppm, about 15 to 40 ppm, or about 20 to 30 ppm. Specific examples of solutions of Petition 870210111885, dated 02 / 12 / 2021, p. 32 / 91 / 62 modified steviol glycoside in which steviol glycoside is present at flavoring levels including 15 to 80 ppm, for example, 16 to 65 ppm total rebaudioside M and rebaudioside A or about 20 to 24 ppm rebaudioside M.
[0066] Other modified steviol glycoside solutions may have higher concentrations of steviol glycoside that may provide a perceptible sweetness, for example, from about 100 ppm to about 5000 ppm, from about 200 ppm to about 5000 ppm, from 300 ppm to about 5000 ppm, from 400 ppm to about 5000 ppm, from 500 ppm to about 5000 ppm, from 600 ppm to about 5000 ppm, from 700 ppm to about 5000 ppm, from 800 ppm to about 5000 ppm, from 900 ppm to about 5000 ppm or from 1000 ppm to about 5000 ppm. In other respects, steviol glycoside is present in a concentration of about 1,000 ppm to about 5,000 ppm, about 2,000 ppm to about 5,000 ppm, about 3,000 ppm to about 5,000 ppm, or about 4,000 ppm to about 5,000 ppm. Steviol glycoside may be present in the modified steviol glycoside solution at a concentration greater than approximately 10, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10.000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000 or 300,000 ppm.
[0067] In another aspect, steviol glycoside is present in the modified steviol glycoside solution at a concentration in the range of about 10 ppm to about 1,000 ppm, more specifically from about 10 ppm to about 800 ppm, from about 50 ppm to about 800 ppm, from about 50 ppm to about 600 ppm, or from about 200 ppm to about 500 ppm. In certain commercially useful implementations, for example, in a ready-to-drink beverage, the concentration of steviol glycoside in the modified steviol glycoside solution may be from 100 ppm to 1,600 ppm, preferably from 200 ppm to 1,000 ppm, or more preferably from Petition 870210111885, dated 02 / 12 / 2021, p. 33 / 91 / 62 400 ppm to 800 ppm.
[0068] The modified steviol glycoside solution may have any suitable pH, for example, between 0 and 7, between 1 and 6, or between 1.5 and 4.
[0069] The amount of bubble modifier in the modified steviol glycoside solution may vary depending on the desired use. For example, the bubble modifier may be present in the modified steviol glycoside solution at about 1 to about 1,000 ppm, about 1 ppm to about 10,000 ppm, about 1 ppm to about 100,000 ppm, about 1 ppm to about 200,000 ppm, or about 1 ppm to about 300,000 ppm. In some respects, the bubble modifier may be present in the modified steviol glycoside solution at about 100 ppm to about 5,000 ppm, about 200 ppm to about 5,000 ppm, 300 ppm to about 5,000 ppm, 400 ppm to about 5,000 ppm, 500 ppm to about 5,000 ppm, 600 ppm to about 5,000 ppm, 700 ppm to about 5,000 ppm, 800 ppm to about 5,000 ppm, 900 ppm to about 5,000 ppm or 1.000 ppm to about 5,000 ppm. In some aspects, the bubble modifier may be present in the modified steviol glycoside solution at about 1,000 ppm to about 5,000 ppm, about 2,000 ppm to about 5,000 ppm, about 3,000 ppm to about 5,000 ppm, or about 4,000 ppm to about 5,000 ppm. In some respects, the bubble modifier may be present in the modified steviol glycoside solution at or greater than approximately 10, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000 ppm. In some respects, the bubble modifier may be present in the modified steviol glycoside solution at or greater than about 200,000 ppm. In some respects, the bubble modifier may be present in the modified steviol glycoside solution at or greater than about 300,000 ppm.
[0070] In an aqueous solution, whether it is a glycoside solution of Petition 870210111885, dated 02 / 12 / 2021, p. 34 / 91 / 62 modified steviol or a gaseous aqueous solution, the bubble modifier compounds may be present in acidic form or in a salt form, for example, as a quaternary ammonium, sodium, potassium, lithium, magnesium or calcium salt or a combination of such salts. In an aqueous solution, the bubble modifier may be dissociated or undissociated, for example, part or all of a potassium salt of an acid bubble modifier compound may be dissociated into a potassium cation and an anion.
[0071] The ratio of bubble modifier to steviol glycoside in the modified steviol glycoside solution may vary. The ratio of bubble modifier to steviol glycoside in the modified steviol glycoside solution may be varied as desired or necessary to make it effective in reducing bubble size in the liquid matrix of the modified steviol glycoside solution or to improve the foaming characteristics of the modified steviol glycoside solution. For example, the ratio of bubble modifier to steviol glycoside may be from about 0.1 to 10. In some respects, the ratio of bubble modifier to steviol glycoside may be between about 0.1 and 5, between about 0.5 and 4, or between about 1 and 3.
[0072] In some aspects, the modified steviol glycoside solution comprises primarily water. The modified steviol glycoside solution may also be buffered with any suitable buffering system, including, but not limited to, one or more buffers such as phosphate, citrate, ascorbate, lactate, acetate, and the like. The buffer may comprise 1 to 1,000 mM of the anion component. In other aspects, the modified steviol glycoside solution comprises a citrate / phosphate buffer. In some aspects, the citrate / phosphate buffer may have a pH of 2 to 4.
[0073] In some respects, the steviol glycoside solution Petition 870210111885, dated 02 / 12 / 2021, page 35 / 91 / 62, as amended, may include additives, flavorings, colorings, fillers, bulking agents, and other ingredients. A wide variety of such ingredients are known for various applications.
[0074] In one aspect, the modified steviol glycoside solution is a beverage product comprising steviol glycoside and a bubble modifier. As used herein, beverage product means a ready-to-drink beverage, a beverage concentrate, a beverage syrup, a frozen beverage, or a powdered beverage. Suitable ready-to-drink beverages include carbonated and non-carbonated beverages. Carbonated beverages include, but are not limited to, carbonated and nitrogenated beverages, such as fortified carbonated beverages, cola, flavored carbonated beverages, such as lemon-lime and orange flavored carbonated beverages, ginger ale, soft drinks, root beer, vanilla flavored soft drinks, and fortified carbonated beverages.Non-carbonated beverages include, but are not limited to, fruit juice, fruit-flavored juice, juice drinks, nectars, vegetable juice, vegetable-flavored juice, sports drinks, energy drinks, fortified water drinks, vitamin-enriched water, near-water drinks (e.g., water with natural or synthetic flavorings), coconut water, tea-type drinks (e.g., black tea, green tea, red tea, oolong tea), coffee, chocolate drinks, drinks containing milk components (e.g., milk drinks, coffee containing milk components, coffee with milk, tea with milk, milk and fruit drinks), drinks containing cereal extracts, smoothies (non-alcoholic, creamy blended drinks containing fruit mixed with milk or yogurt) and combinations thereof.
[0075] Beverage concentrates and beverage syrups can be prepared with an initial volume of liquid matrix (e.g., water) and the desired beverage ingredients. Maximum concentration beverages are Petition 870210111885, dated 02 / 12 / 2021, pages 36 / 91 / 62, prepared by adding additional volumes of water.
[0076] In some respects, a beverage concentrate can be used as a diluting syrup to prepare a gaseous aqueous solution, such as a carbonated soft drink prepared in a soda machine. The modified steviol glycoside solution may comprise primarily water, but may also include alcohol.
[0077] The modified steviol glycoside solution may also comprise a buffer such as a citrate / phosphate buffer. The citrate / phosphate buffer may have a pH of 1.5 to 4, for example, 2 to 4.
[0078] In some respects, the beverage concentrate solution is diluted before use as a beverage, for example, in a soda machine by dilution with a stream of carbonated water as the beverage is dispensed to form a gaseous aqueous solution. The volume of the final diluted beverage may be much greater than the concentrate, for example, 5 to 7 times (in the case of a typical diluting syrup) or 80 to 100 times (in the case of a typical liquid enhancer) the volume of the beverage concentrate solution in that beverage. The bubble modifier may be present in the beverage concentrate in an amount effective to improve the foaming properties as the beverage is dispensed. Such a beverage concentrate useful as a diluting syrup may have about 1,500 to 4,200 ppm of steviol glycoside and 1,800 to 5,400 ppm, for example, 1,800 to 3,000 ppm of bubble modifier.If the beverage concentrate is to be used as a liquid enhancer that is diluted 80 to 100 times in the final beverage, it may contain approximately 4,800 to 20,000 ppm, for example, 6,000 to 10,000 ppm, of steviol glycoside and 2,400 to 20,000 ppm, for example, 3,000 to 10,000 ppm, of bubble modifier.
[0079] Modified steviol glycoside solutions can be non-alcoholic or alcoholic. A non-alcoholic modified steviol glycoside solution, for example, a non-alcoholic beer, can Petition 870210111885, dated 02 / 12 / 2021, page 37 / 91 / 62, contain less than 0.5% (by weight), preferably less than 0.2% (by weight), less than 0.1% (by weight) or less than 0.05% (by weight), for example, 0% (by weight) of ethanol. Alcoholic solutions of modified steviol glycoside may contain more than 0.5% (by weight) of alcohol, for example, 2 to 60% (by weight). However, some bubble modifier compounds may not be very soluble in alcohol. An alcoholic solution of modified steviol glycoside may have the bubble modifier up to a solubility limit of some or all of its constituent bubble modifier compounds. In order to retain some useful bubble modifiers in solution, the alcohol content of an alcoholic modified steviol glycoside solution can be maintained at a relatively low level of 1 to 5% (by weight) alcohol.
[0080] Bubble modifiers in aqueous solutions without steviol glycoside compounds do not have a very large impact on the foaming behavior of such aqueous solutions. Steviol glycoside compounds in aqueous solutions without bubble modifiers affect the foaming behavior of such aqueous solutions. We found, however, that modified solutions that include steviol glycoside, for example, sweetening levels of steviol glycoside compounds, and bubble modifiers described herein have a dramatic impact on foaming behavior.
[0081] Such modified steviol glycoside solutions with modified foaming properties can produce more foam, a more stable foam, and / or a foam with reduced bubble size. This can be commercially attractive in a variety of applications. For example, a larger foam volume and / or a more stable foam can be particularly visually appealing for carbonated beverages such as root beer; beer, which is typically carbonated with carbon dioxide or, increasingly, nitrogen or Petition 870210111885, dated 02 / 12 / 2021, page 38 / 91 / 62 combinations of carbon dioxide and nitrogen; and to provide non-alcoholic beer, more than one head so that they look more like conventional beer.
[0082] In one aspect, modified steviol glycoside solutions according to the disclosure have at least 20 ppm, preferably at least 50 ppm, or at least 100 ppm of steviol glycoside and a bubble modifier at a concentration of 50 ppm to 1,600 ppm. The concentration of the bubble modifier in the modified steviol glycoside solution must be effective in reducing the average bubble diameter in the foam compared to the aqueous solution without the bubble modifier. Foam may be formed natively by effervescence of gas dissolved in the modified steviol glycoside solution if it is a carbonated aqueous solution. Foam may form in other ways, alone or in addition to effervescence.For example, foam can be formed by mixing the modified steviol glycoside solution with carbonated water in a soda machine, by agitation, for example, by mixing in a mixer or stirring, or by bubbling gas through the modified steviol glycoside solution.
[0083] A standardized test protocol for determining whether a modified steviol glycoside solution has an amount of bubble modifier effective in modifying a foam in a desired manner (e.g., reducing the size of bubbles in the foam by at least 5%) is referred to in the present invention as the Foamscan test. This test is conducted on a commercially available Foamscan instrument from Teclis Scientific. The Foamscan analyzes the foam behavior by injecting or bubbling gas through a volume of liquid and measuring the volume of foam generated by the sprayed gas, the stability of that foam, and / or visual characterization of the foam. The Foamscan is performed by releasing air for 60 seconds to 60 mL of the steviol glycoside solution. Petition 870210111885, dated 02 / 12 / 2021, pp. 39 / 91 34 / 62 modified steviol at an airflow rate of 150 mL / minute. The temperature of the modified steviol glycoside solution should be 15.6 °C (60 °F) and the test should be conducted at an ambient pressure of 1 atmosphere.
[0084] As explained in Example 1 below, the Foamscan instrument performing the Foamscan test can determine the average bubble area in the foam through a digital photograph of the foam and image analysis. The photograph is two-dimensional, so the bubble size is measured as the bubble area in the image. To determine the average bubble diameter, it can be assumed that the bubbles have a shape close to a sphere, which would be reflected as a circle in two dimensions. The diameter can be readily derived from the bubble area in the image: (area -
[0085] A useful modified steviol glycoside solution has an amount of bubble modifier that is effective, in the presence of the steviol glycoside, in reducing the average bubble diameter in the foam compared with the foam bubbles in an aqueous control solution without the bubble modifier (i.e., an aqueous solution having the same composition except for the omission of the bubble modifier). The average bubble diameter in the Foamscan test is desirably at least 5%, at least 10%, or at least 15%, preferably at least 20%, at least 25%, at least 30%, at least 40%, or at least 50% smaller in the modified steviol glycoside solution than the average bubble diameter in the control solution.
[0086] The Foamscan instrument also determines foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (teSpumai / 2). Example 1 defines each of these measurements. Petition 870210111885, dated 02 / 12 / 2021, pages 40 / 91 / 62
[0087] Modified steviol glycoside solutions suitable for certain commercial applications may have a foaming capacity (defined below) of at least 0.8, determined using the maximum foam volume obtained during sample passage. Alternatively, the foaming capacity may be determined using volumes measured 30 seconds after the end of gas release (called FC30). Some of these solutions may have a foaming capacity or FC30 of at least 0.9, at least 1.0, at least 1.1, or at least 1.2.
[0088] Viewed from another perspective, modified steviol glycoside solutions according to aspects of this disclosure may have a foaming capacity or FC30 of at least 40%, preferably at least 60%, at least 70%, at least 75%, or at least 80% greater than the foaming capacity or FC30, respectively, of a control aqueous solution without the bubble modifier.
[0089] The foaming test does not directly characterize the foam that may form in a solution in use, for example, when dispensing carbonated cola from a soda machine or mixing a frozen beverage in a mixer. However, it is believed to provide valuable quantitative insight into the foaming characteristics of a beverage that can generally correlate with foaming behavior in real-world use situations.
[0090] As discussed in the examples below, non-carbonated beverages with different compositions were analyzed using the Foamscan test, including flavored and unflavored non-carbonated water (still water). Samples of non-carbonated water were prepared with steviol glycoside and bubble modifier (SG + BM), with steviol glycoside but without the bubble modifier (SG), and with bubble modifier but without steviol glycoside (BM). The average final foam volumes (Vfoam) were 82 for the SG samples, only 19 for the BM samples, but Petition 870210111885, dated 02 / 12 / 2021, pages 41 / 91 / 62 161 for the SG + BM samples. This demonstrates a significant and unexpected synergy between the bubble modifier and the steviol glycoside. In certain respects, the Vespuma in a modified steviol glycoside solution as measured using the Foamscan test is at least 20% greater, at least 25% greater, or at least 30% greater, preferably at least 40% greater, at least 50% greater, or at least 60% greater than the Vespuma for a first control solution having the same composition without the bubble modifier, than the Vespuma for a second control solution having the same composition without the steviol glycoside, or than the Vespuma for both the first and second controls. Aqueous carbonated solutions
[0091] Other aspects of the disclosure provide carbonated aqueous solutions that include a bubble modifier, but may or may not include steviol glycoside. Examples of carbonated aqueous solutions without steviol glycoside include flavored carbonated waters and conventional ready-to-drink soft drinks, such as a cola or energy drink, sweetened with sugar, aspartame, or another non-steviol glycoside sweetener.
[0092] Gaseous aqueous solutions can be carbonated with any gas suitable for the intended purpose. Beverages, for example, are conventionally carbonated with carbon dioxide and / or nitrogen.
[0093] The amount of dissolved gas in the aqueous gaseous solution can vary widely, but it must be sufficient for the aqueous gaseous solution to effervesce at STP. The gas in the modified steviol glycoside solution can be at a level at least 50%, preferably at least 100%, at least 200%, or at least 300% higher than an equilibrium saturation value of the gas at STP. Nitrogen has limited solubility in most aqueous solutions. Consequently, it may be desirable to include Petition 870210111885, of 02 / 12 / 2021, p. 42 / 91 / 62 nitrogen and carbon dioxide, for example, with nitrogen at its maximum solubility and the desired roughness balance coming from CO2.
[0094] The bubble modifier may be present in an amount effective to reduce the average diameter of the bubbles in the matrix of the modified steviol glycoside solution, or coalesced on a surface of the container for the modified steviol glycoside solution, relative to a control solution without the bubble modifier (i.e., an aqueous solution having the same composition but omitting the bubble modifier). In one aspect, the term in the matrix is intended to indicate bubbles within the body of the solution, rather than in a foam carried by the solution.
[0095] The average bubble size may be reduced over a long period or even until one of the modified steviol glycoside solutions and the control solution no longer effervesces. Comparing the bubble diameter at a fixed time, however, may allow for more reproducible results. Thus, in one aspect, the bubble sizes in the modified steviol glycoside solution and the control are measured at STP within 1 minute of the onset of effervescence. It may be difficult, if not impossible, to measure bubble size in a can or bottle. Therefore, a carbonated canned or bottled beverage can be poured into a container more suitable for bubble size measurement, and the onset of effervescence will be adjusted as the time the beverage is poured into the container.Some aqueous gaseous solutions can be formed by injecting gas into the solution, for example, by injecting nitrogen with a restriction plate into a line through which the solution flows, or by adding carbonated water (or other suitable liquid), for example, as in a conventional soda machine. In such circumstances, the onset of effervescence will be defined as the moment when the dispensing of the solution into a measuring container is complete. Petition 870210111885, dated 02 / 12 / 2021, pages 43 / 91 / 62
[0096] Although bubbles in a gaseous solution may come from other sources, such as agitation or bubbling, the bubbles measured to determine the average diameter must be bubbles native to the gaseous aqueous solution, that is, they arise from the gas dissolved in the solution.
[0097] Bubbles formed in aqueous gaseous solutions that include a bubble modifier may have other useful attributes. For example, bubbles may persist longer in the solution matrix or on a container surface in an aqueous gaseous solution with a bubble modifier than in the same aqueous gaseous solution without the bubble modifier. Bubbles may also have a slower release time from a container surface in an aqueous gaseous solution with a bubble modifier than in the same aqueous gaseous solution without the bubble modifier. This can produce a more visually appealing aqueous gaseous beverage that includes a bubble modifier because it appears more bubbly than the same beverage without the bubble modifier. Methods
[0098] A method for reducing the size of bubbles formed by a gasified aqueous solution, wherein the method comprises adding a bubble modifier to an aqueous solution after, or more desirably before or at the time of gasification of the aqueous solution.
[0099] A method for increasing the volume, volumetric stability, foaming capacity, foam expansion, and / or foam density of a foam produced from an aqueous solution, wherein the method comprises adding a bubble modifier and a steviol glycoside to an aqueous solution after, or more desirably before or at the time of gasification of the aqueous solution. Examples
[00100] The following examples are provided to illustrate the disclosure, but are not intended to limit its scope. All parties and Petition 870210111885, dated 02 / 12 / 2021, pp. 44 / 91 39 / 62 percentages are expressed by weight except where otherwise indicated. Example 1: Protocol 1
[00101] Protocol 1 used a fixed air-gas bubbling time of 40 s or 60 s to analyze the properties of the respective samples. Briefly, measurements were performed with a Foamscan™ instrument (Teclis Scientific, Marseille, France). An initial liquid volume of 60 mL from an individual liquid sample was loaded into the vertical glass cylinder of the Foamscan™ instrument. Air gas was then sprayed onto the liquid sample at a gas flow rate of 150 mL / min for 40 s or 60 s to generate foam. The generated foam expanded above the surface of the liquid sample inside the vertical glass cylinder. Foam generation and foam decomposition were monitored in real time from the start of air gas injection until complete decomposition of the generated foam. The volume of foam generated was measured in real time. Foam conductance was also measured in real time.
[00102] Foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (tespumai / 2) were determined.
[00103] Foam capacity (FC) at time t was calculated as a total volume of foam (Vt(foam)) at time t relative to a total volume of sprayed gas (Vt(gas)) as follows: , Vt(esvuma) pc(t) = —5 .
[00104] The maximum foam density (MD) was calculated using an initial liquid volume (Vi(liquid)), a final liquid volume (Vf(liquid)), and a final foam volume (Vffoam)) as follows: FiCíq-uid o) — K / Gíquido) (Vflespuma) Petition 870210111885, dated 02 / 12 / 2021, pp. 45 / 91 40 / 62
[00105] Foam expansion (FE) was calculated using the final foam volume (Vf(foam)), the initial liquid volume (Vi(liquid)), and the final liquid volume (Vf(liquid)) as follows: Vf {foam) —--------------Vi{liquid) — Vf {liquid)
[00106] The final foam capacity (FC) was calculated as the final volume of the foam (Vf(foam)) relative to the final volume of the sprayed gas (Vf(gas)) as follows: Vf {foam}FCVf{pks}
[00107] The volumetric stability of the foam (teSpumai / 2) was determined as the time required for the foam volume to decompose by half. The largest measured foam volume was used as the final foam volume (Vf(foam)). The total amount of gas that was sprayed was used as the final volume of gas injected (Vf(gas)). The initial volume of the liquid sample that was loaded into the instrument was used as the initial liquid volume (Vi(liquid)). The volume of liquid at the moment when the foam volume reached its highest measurement was the final liquid volume (Vf(liquid)). The final conductance of the foam was measured at the moment when the generated foam reached its largest volume. Protocol 2
[00108] Protocol 2 used air gas bubbling to create a fixed volume of foam to analyze the properties of the respective samples. Briefly, measurements were performed with a Foamscan™ foam analyzer (Teclis Scientific, Marseille, France). An initial liquid volume of 60 mL of sample was loaded into the vertical glass cylinder of the Foamscan instrument. Air gas was then sprayed onto the liquid sample at a gas flow rate of 150 mL / min to generate foam. The generated foam expanded above the surface of the liquid sample, and air gas bubbling continued until 250 mL of foam was obtained. Petition 870210111885, dated 02 / 12 / 2021, pp. 46 / 91 / 62 generated. Foam generation and foam decomposition were monitored in real time from the beginning of air gas bubbling until the complete decomposition of the generated foam. The volume of foam generated was measured in real time. Foam conductance was also measured in real time. Foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (tespuma1 / 2) were determined as described for Protocol 1. Example 2: Sample preparation
[00109] Samples corresponding to diet drinks were prepared with combinations of steviol glycoside, bubble modifier, citrate buffer, and / or flavorings. High-purity rebaudioside M was used (>95% total steviol glycoside compounds (JECFA 9 + rebaudioside M) comprising ~87.5% rebaudioside M and ~10.4% rebaudioside D). The bubble modifier was a botanical extract derived from mating herb (Cargill lot no. YM20180628) as described above. The bubble modifier comprised more than 40% dicaffeoylquinic acids and / or their salts. Samples A, B, C, D, and E had the steviol glycoside concentrations, bubble modifier concentrations, and flavorings as shown in Table 1. Table 1. Sample Description Steviol glycoside concentration (ppm) Bubble modifier concentration (ppm) Flavoring A Unflavored diet (RebM) 500 0 none B Unflavored diet (Bubble modifier) 0 250 none C Unflavored diet (RebM + bubble modifier) 500 250 none D Lemon-Sicilian / Lime-Tahitian diet (RebM + bubble modifier) 500 250 Lemon-Sicilian / Lime-Tahitian Petition 870210111885, dated 02 / 12 / 2021, pages 47 / 91 / 62 E Diet Cola (RebM + bubble modifier) 700 475 Cola
[00110] Samples A, B, C, D, and E were prepared with the components shown in Table 2 and water added to the volume. As indicated below, samples A, B, C, D, and E were each pH buffered with an acid citrate buffering system. Table 2. Ingredient Description Supplier Sample A Sample B Sample C Sample D Sample E Steviol glycoside Cargill 0.05% (500 ppm) - 0.05% (500 ppm) 0.05% (500 ppm) 0.07% (700 ppm) Bubble modifier Cargill - 0.025% (250 ppm) 0.025% (250 ppm) 0.025% (250 ppm) 0.0475% (475 ppm) Citric acid, anhydrous Cargill 0.098% 0.098% 0.098% 0.098% - Potassium citrate, monohydrate Cargill 0.026% 0.026% 0.026% 0.026% - Sodium benzoate Spectrum 0.015% 0.015% 0.015% 0.015% 0.025% Natural Sicilian lemon flavor - - - 0.180% - Cola flavor Givaudan 0.19% Caffeine, anhydrous SAFC 0.0095%
[00111] Sample A was prepared by preheating water to approximately 20% of the desired final volume to 65 °C, adding the corresponding amount of Reb M to the preheated water, covering it, and allowing the Reb M to dissolve while stirring with a magnetic stir bar on a stirring plate. After the Reb M had dissolved, the remaining ingredients were added in the following order while stirring: sodium benzoate, potassium citrate, and citric acid. Water (20 °C) was added to the desired final volume, and the sample was stirred until completely dissolved. The sample had a pH of 3.2. The sample was transferred to a 12-fluid-ounce glass bottle, labeled, and sealed.
[00112] Sample B was prepared by preheating water in an amount of approximately 20% of the desired final volume to 40°C, adding the corresponding amount of bubble modifier to the preheated water, covering it, and allowing the bubble modifier to dissolve while Petition 870210111885, dated 02 / 12 / 2021, pp. 48 / 91 / 62, was stirred with a magnetic stirring bar on a stirring plate. After the bubble modifier dissolved, the remaining ingredients were added in the following order while stirring: sodium benzoate, potassium citrate, and citric acid. Water (20 °C) was added to the desired final volume, and the sample was stirred until completely dissolved. The sample had a pH of 3.2. The sample was transferred to a 12-fluid-ounce glass bottle, labeled, and sealed.
[00113] Sample C was prepared by preheating water to approximately 20% of the desired final volume to 40 °C, adding the corresponding amount of bubble modifier to the preheated water, covering, and allowing the bubble modifier to dissolve while stirring with a magnetic stir bar on a stirring plate. The corresponding amount of Reb M was then added and stirred until dissolved. After the Reb M dissolved, the remaining ingredients were added in the following order while stirring: sodium benzoate, potassium citrate, and citric acid. Water (20 °C) was added to the desired final volume, and the sample was stirred until completely dissolved. The sample had a pH of 3.2. The sample was transferred to a 12-fluid-ounce glass bottle, labeled, and sealed.
[00114] Sample D was prepared by preheating water to approximately 20% of the desired final volume to 40 °C, adding the corresponding amount of bubble modifier to the preheated water, covering, and allowing the bubble modifier to dissolve while stirring with a magnetic stir bar on a stirring plate. The corresponding amount of Reb M was then added and stirred until dissolved. After the Reb M dissolved, the remaining ingredients were added in the following order while stirring: sodium benzoate, potassium citrate, citric acid, and lemon-lime-Sicilian flavoring. Water (20 °C) was added to the desired final volume and the sample was stirred until... Petition 870210111885, dated 02 / 12 / 2021, page 49 / 91 / 62 completely dissolved. The sample had a pH of 3.2. The sample was transferred to a 12 fluid ounce glass bottle, labeled and sealed.
[00115] Sample E was prepared by preheating water in an amount of approximately 20% of the desired final volume to 40 °C, adding the corresponding amount of bubble modifier to the preheated water, covering, and allowing the bubble modifier compound to dissolve while stirring with a magnetic stirring bar on a stirring plate. The corresponding amount of Reb M was then added and stirred until dissolved. After the Reb M dissolved, the remaining ingredients were added in the following order while stirring: sodium benzoate and cola flavoring. Phosphoric acid was added until a pH of 2.9 to 3.1 was reached. Water (20 °C) was added to the desired final volume and the sample was stirred until completely dissolved.The sample had a pH between 2.9 and 3.1. The sample was transferred to a 12-fluid-ounce glass bottle, labeled, and sealed. Example 3:
[00116] Samples A, B, C, D, and E were prepared as described in Example 2. Protocol 1, using an air gas bubbling time of 40 s 150 mL / min, was run to analyze the foam properties of each of the individual samples A to E. Several measurements were performed for each individual sample. The initial liquid volume was 60 mL. Air was used as the sprayed gas. Foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (tespuma1 / 2) were determined for each of the samples A to E. The final foam conductance was also measured.
[00117] The results for Protocol 1 (40 s of air gas bubbling) are shown in Table 3. Table 3 - Protocol 1, 40 s of air bubbling Petition 870210111885, dated 02 / 12 / 2021, pages 50 / 91 / 62 Sample A (RebM) B (Bubble modifier) C (RebM, bubble modifier) D (RebM, bubble modifier, Sicilian lemon-Tahitian lime) E (RebM, bubble modifier, glue) Number of measurements 3 3 2 2 3 Gas flow rate (mL / min) 150 150 150 150 150 Total gas bubbling time (s) 40 40 40 40 40 Final foam volume (mL) 66 (SD=10) 23 (SD=1) 118 (SD=2) 118 (SD=0) 119 (SD=3) Final foam conductance (gS) 42.5 0.125 58.242 65.47 80.41 Total gas volume (mL) 97 97 97 97 97 Foam Expansion (FE) 4.6 14.6 4.8 3.6 4 Foam Capacity (FC) 0.68 0.23 1.22 1.22 1.23 Maximum Foam Density (MD) 0.223 0.069 0.245 0.281 0.253 Volumetric Foam Stability (s) 14 (SD=2.1) 7.5 (SD=0.6) 104 (SD=10) 180 (SD=18) 221 (SD=10) Foam Conductance Stability (s) 6 0 21.5 32 28.5
[00118] The final foam volumes of Sample A (RebM) and Sample B (bubble modifier) were 66 mL and 23 mL, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-calité flavoring), and E (RebM, bubble modifier, cola flavoring) had final foam volumes of 118 mL, 118 mL, and 119 mL, respectively. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam volumes compared to the sample with only steviol glycoside. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam volumes compared to the sample with only bubble modifier. The final foam volumes for the samples comprising both steviol glycoside and bubble modifier were approximately twice the final foam volume of Petition 870210111885, dated 02 / 12 / 2021, page 51 / 91 / 62 sample with only steviol glycoside. The final foam volumes for the samples comprising both steviol glycoside and bubble modifier were approximately five times the final foam volume of the sample with only bubble modifier.
[00119] The final foam capacities of sample A (RebM) and sample B (bubble modifier) were 0.68 and 0.23, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-lime flavoring), and E (RebM, bubble modifier, cola flavoring) had final foam capacities of 1.22, 1.22, and 1.23, respectively. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam capacity compared to the sample with only steviol glycoside. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam capacity compared to the sample with only bubble modifier.The final foam capacities for samples comprising both steviol glycoside and bubble modifier were almost twice the final foam capacities of the sample with only steviol glycoside. The final foam capacities for samples comprising both steviol glycoside and bubble modifier were approximately five times the final foam capacity of the sample with only bubble modifier.
[00120] The final foam conductance of sample A (RebM) and sample B (bubble modifier) was 42.5 pS and 0.125 pS, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-Sicilian flavoring), and E (RebM, bubble modifier, cola flavoring) had final foam conductances of 58.242 pS, 65.47 pS, and 80.41 pS, respectively. Each of the samples comprising both steviol glycoside and bubble modifier. Petition 870210111885, dated 02 / 12 / 2021, pp. 52 / 91 / 62, showed surprising increases in final foam conductance compared to the sample with steviol glycoside only. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam conductance compared to the sample with bubble modifier only. The final foam capacities for the samples comprising both steviol glycoside and bubble modifier were increased relative to the final foam conductances of the sample with steviol glycoside only.
[00121] The volumetric foam stabilities of sample A (RebM) and sample B (bubble modifier) were 14 s and 7.5 s, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-lime flavoring), and E (RebM, bubble modifier, cola flavoring) showed volumetric foam stabilities of 104 s, 180 s, and 221 s, respectively. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in volumetric foam stability compared to the sample with only steviol glycoside. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in volumetric foam stability compared to the sample with only bubble modifier.The volumetric stabilities of the foam for the samples comprising steviol glycoside and bubble modifier were between approximately 7 and 16 times longer than the volumetric stability of the foam for the sample with only steviol glycoside. The volumetric stabilities of the foam for the samples comprising steviol glycoside and bubble modifier were between approximately 13 and 29 times longer than the volumetric stability of the foam for the sample with only bubble modifier. The volumetric stability for samples D and E was longer than the volumetric stability of the foam for the sample without. Petition 870210111885, dated 02 / 12 / 2021, page 53 / 91 / 62 flavoring, sample C. Sample E (cola flavoring) had a longer volumetric foam stability (221 s) than sample D (lemon-Sicilian-lime-Tahitian flavoring) (180 s). Example 4:
[00122] Samples A, B, C, D, and E were prepared as described in Example 2. Protocol 1, using an air gas bubbling time of 60 s 150 mL / min, was run to analyze the foam properties of each of the individual samples A to E. Several measurements were performed for each individual sample. The initial liquid volume was 60 mL. Air was used as the sprayed gas. Foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (tespuma1 / 2) were determined for each of the samples A to E. The final foam conductance was also measured.
[00123] The results for Protocol 1 (60 s of air gas bubbling) are shown in Table 4. Table 4 - Protocol 1, 60 s of air bubbling_____________________ Sample ABCDE Number of measurements 3 1 3 2 3 Gas flow rate (mL / min) 150 150 150 150 150 Total gas bubbling time (s) 60 60 60 60 60 Final foam volume (mL) 82 (SD=4) 19 161 (SD=3) 174 (SD=6) 170 (SD=2) Final foam conductance (gS) 43.600 0.192 47.981 76.210 67.613 Total gas volume (mL) 147 147 147 147 147 Foam expansion (FE) 5 19.3 4.8 3.5 4.43 Foam capacity (FC) 0.56 0.13 1.097 1.19 1.153 Maximum foam density (MD) 0.198 0.052 0.207 0.289 0.255 Volumetric foam stability (s) 17 (SD=1) 11 49 (SD=4) 90 (SD=3) 53 (SD 11) Foam conductance stability (s) 5 0 10 13 10
[00124] The final foam volumes of sample A (RebM) and sample B (bubble modifier) were 82 mL and 19 mL, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-Sicilian-lime-Tahitian flavoring) and E (RebM, bubble modifier) Petition 870210111885, dated 02 / 12 / 2021, pp. 54 / 91 / 62. The final foam volumes for the samples containing both steviol glycoside and bubble modifier were approximately twice the final foam volume of the sample containing only steviol glycoside. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam volumes compared to the sample with only steviol glycoside.The final foam volumes for the samples containing both steviol glycoside and bubble modifier were more than 8 times the final foam volume of the sample with bubble modifier alone.
[00125] The final foam capacities of sample A (RebM) and sample B (bubble modifier) were 0.56 and 0.13, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-lime flavoring), and E (RebM, bubble modifier, cola flavoring) had final foam capacities of 1.097, 1.19, and 1.153, respectively. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam capacity compared to the sample with only steviol glycoside. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam capacity compared to the sample with only bubble modifier.The final foam capacities for the samples comprising both steviol glycoside and bubble modifier were approximately twice the final foam capacities of the sample with only steviol glycoside. Final capacities. Petition 870210111885, dated 02 / 12 / 2021, page 55 / 91 / 62, the foam capacity for samples containing both steviol glycoside and bubble modifier was more than 8 times the final foam capacity of the sample with only bubble modifier.
[00126] The final foam conductance of sample A (RebM) and sample B (bubble modifier) was 443.600 pS and 0.192 pS, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-lime flavoring), and E (RebM, bubble modifier, cola flavoring) had final foam conductances of 47.981 pS, 76.210 pS, and 67.613 pS, respectively. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam conductance compared to the sample with only steviol glycoside. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in final foam conductance compared to the sample with only bubble modifier.The final foam conductances for samples containing both steviol glycoside and bubble modifier were increased compared to the final foam capacities of the sample with steviol glycoside alone.
[00127] The volumetric foam stabilities of sample A (RebM) and sample B (bubble modifier) were 17 s and 11 s, respectively. Samples C (RebM, bubble modifier), D (RebM, bubble modifier, lemon-lime-lime flavoring), and E (RebM, bubble modifier, cola flavoring) showed volumetric foam stabilities of 49 s, 90 s, and 53 s, respectively. Each of the samples comprising both steviol glycoside and bubble modifier showed surprising increases in volumetric foam stability compared to the sample with only steviol glycoside. Each of the samples comprising both steviol glycoside and Petition 870210111885, dated 02 / 12 / 2021, pp. 56 / 91 / 62: The bubble modifier showed surprising increases in volumetric foam stability compared to the sample with only the bubble modifier. The volumetric foam stabilities for the samples comprising steviol glycoside and bubble modifier were between approximately 2 and 5 times longer than the volumetric foam stability of the sample with only steviol glycoside. The volumetric foam stabilities for the samples comprising steviol glycoside and bubble modifier were between approximately 4 and 8 times longer than the volumetric foam stability of the sample with only bubble modifier. The volumetric stability for samples D and E was longer than the volumetric foam stability of the unflavored sample, sample C.Sample D (cola flavoring) had a longer volumetric foam stability (90 s) than sample E (lemon-Sicilian-lime-Tahitian flavoring) (53 s). Example 5:
[00128] Samples A, B, C, D, and E were prepared as described in Example 2. Protocol 2, using an air gas bubbling rate of 150 mL / min to obtain a volume of 250 mL of generated foam, was performed to analyze the foam properties of each of the individual samples A to E. Several measurements were taken for each individual sample. The initial liquid volume was 60 mL. Air was used as the sprayed gas. Foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (tespuma1 / 2) were determined for each of the samples A to E. The final foam conductance was also measured.
[00129] The results for Protocol 2 are shown in Table 5. Table 5 - Protocol 2, 250 mL foam height ____________________ Sample ABCDE Number of measurements 1 0 1 1 1 Petition 870210111885, dated 02 / 12 / 2021, pages 57 / 91 / 62 Gas flow rate (mL / min) 150 - 150 150 150 Total gas bubbling time (s) 68 - 133 (89s) 87 91 Final foam volume (mL) 90 - 195 (adjusted to 250) 250 250 Final foam conductance (μS) 45.511 - 76.55 81.436 101.518 Total gas volume (mL) 167 - 330 215 222 Foam expansion (FE) 5.6 - 4.4 4.6 6 Foam capacity (FC) 0.54 - 0.38 1.17 1.1 Maximum foam density (MD) 0.179 - 0.228 0.22 0.165 Volumetric stability of Foam (s) 16 - 20 66 23 Conductance stability of foam (s) 6 - 9 10 11
[00130] As shown in Table 5, due to insufficient foam formation, samples A(RebM), B(bubble modifier), and C(RebM, bubble modifier) did not yield complete data. Sample A only reached a final foam volume of 90 mL after 68 s of total gas bubbling time. Sample B could not be tested due to very little foam generated. Sample C only reached a final foam volume of 195 mL. Therefore, although foam properties were determined for samples A, B, and C, it is difficult to compare these foam properties with the foam properties of samples D and E. Samples D and E generated sufficient foam to reach a fixed foam volume of 250 mL. The final foam capacities for samples D and E were 1.17 and 1.1, respectively. The final foam conductances for samples D and E were 81.436 pS and 101.518 pS, respectively.The volumetric stabilities of the foam for sample D and sample E were 66 s and 23 s, respectively. Example 6:
[00131] In each of Examples 3 to 5, bubble properties were observed by digital photography. Digital photographs of bubbles of Petition 870210111885, dated 02 / 12 / 2021, p. 58 / 91 / 62. Foam samples were taken at regular intervals as air-gas bubbling began, throughout the air-gas bubbling, and during the decomposition of the generated foam. Digital photographs were taken for samples A, C, D, and E. Digital photographs of sample B were not taken because very little foam was generated in the analysis of sample B and the foam decomposition was rapid. Figures 1 to 4C show digital photographs of samples A, C, D, and E. Figure 1 shows digital photographs of bubbles for sample A after 35 s, at 40 s, at 45 s, at 50 s, at 55 s, at 60 s, at 65 s, at 70 s, at 75 s, at 80 s and at 85 s for Example 3. Figure 2A shows digital photographs of bubbles for sample C after 5 s, at 10 s, at 15 s, at 50 s, at 65 s and at 75 s for Example 3.Figure 2B shows digital photographs of bubbles for sample C after 5 s, at 10 s, at 15 s, at 20 s, at 90 s and at 150 s for Example 4. Figure 2C shows digital photographs of bubbles for sample C after 5 s, at 10 s, at 15 s and at 20 s for Example 5. Figure 3A shows digital photographs of bubbles for sample D after 5 s, at 10 s, at 15 s, at 55 s, at 150 s and at 185 s for Example 3. Figure 3B shows digital photographs of bubbles for sample D after 5 s, at 10 s, at 15 s, at 30 s, at 35 s and at 40 s for Example 4. Figure 3C shows digital photographs of bubbles for sample D after 5 s, at 10 s, at Figure 4A shows digital photographs of bubbles for sample E after 5 s, at 10 s, at 15 s, at 150 s, at 300 s and at 450 s for Example 3. Figure 4B shows digital photographs of bubbles for sample E after 5 s, at 10 s, at 15 s, at 30 s, at 35 s and at 40 s for Example 4.Figure 4C shows digital photographs of bubbles for sample E after 5 s, at 10 s, at 15 s, at 30 s, at 35 s and at 40 s for Example 5.
[00132] The average bubble area in each time interval for individual samples was determined from the digital photographs by analysis with software (Cellsize, Teclis Instruments) for Example 3. The average bubble area for each of the samples C, D, and E was determined and the Petition 870210111885, dated 02 / 12 / 2021, page 59 / 91 / 62. The time to reach a bubble area of 0.04 to 0.1 mm² was determined. Table 5 shows the time interval to reach an average bubble area of 0.04 to 0.1 mm² for samples C, D, and E of Example 3. Table 6. Sample Time interval for average bubble area to reach 0.04 to 0.1 mm2 Sample C (unflavored with RebM and bubble modifier) 85-120 s Sample D (lemon-Sicilian-lime-Tahitian with RebM and bubble modifier) 125-150 s Sample E (Cola flavored with RebM and bubble modifier) 215-445 s
[00133] Table 6 shows that the time interval to reach an average bubble area of 0.04 to 0.1 mm2 is longer for samples with flavoring (samples D and E) than for the unflavored sample (sample C). Table 6 also shows that the time interval to reach an average bubble area of 0.04 to 0.1 mm2 is longer for samples with cola flavoring (sample D) than with lemon-lime-lime flavoring (sample E). Example 7:
[00134] Samples corresponding to diet drinks were prepared with combinations of steviol glycoside, bubble modifier and / or flavorings. High-purity rebaudioside M was used (> 95% total steviol glycosides (JECFA 9 + rebaudioside M) comprising ~ 87.5% rebaudioside M and ~ 10.4% rebaudioside D). The bubble modifier was a botanical extract derived from mating herb (Cargill lot no. YM20180628) as described above. The bubble modifier comprised more than 40% dicaffeoylquinic acids and / or their salts. Samples 1 through 9 had the concentrations of steviol glycoside, bubble modifier, orange flavoring, and / or sodium benzoate-based preservative (final concentration 0.015%) as shown below in Table 11. The samples were either unflavored (water) or orange-flavored. The samples were prepared with water. Petition 870210111885, dated 02 / 12 / 2021, pp. 60 / 91 / 62 distilled. The samples were unbuffered, except for sample 5, which had 0.098% anhydrous citric acid and 0.026% potassium citrate monohydrate. Table 11. Sample Description Concentration of RebM (ppm) Concentration of bubble modifier (ppm) Sodium benzoate-based preservative 1 Water (RebM) 500 0 2 Orange flavor (RebM) 500 0 3 Water (bubble modifier) 250 4 Orange flavor (bubble modifier) 250 5 Water (RebM, bubble modifier) 500 250 6 Orange flavor (RebM, bubble modifier) 500 250 7 Water (RebM, bubble modifier, preservative) 500 250 150 ppm 8 Orange flavor (RebM, bubble modifier, preservative) 500 250 150 ppm 9 Acid buffer (RebM, bubble modifier, preservative) 500 250 150 ppm
[00135] Samples 1 to 9 were prepared as described. Protocol 1, using an air gas bubbling time of 40 s 150 mL / min, was run to analyze the foam properties of each of the individual samples 1 to 9. Several measurements were performed for each individual sample. The initial liquid volume was 60 mL. Air, nitrogen gas, and carbon dioxide gas were each used individually as the sprayed gas for each of the samples 1 to 9. Foam capacity (FC), maximum foam density (MD), foam expansion (FE), foam capacity (FC), and volumetric foam stability (tespuma1 / 2) were determined for each of the samples 1 to 9. The final foam conductance was also measured.
[00136] The results for Protocol 1 (40 s of bubbling air, nitrogen gas and carbon dioxide gas) for samples 1 and 2 are shown in Table 12. Petition 870210111885, dated 02 / 12 / 2021, pages 61 / 91 / 62 Table 12. Gas Ar N2 CO2 Ar N2 CO2 Sample 1 (Water, RebM) 1 (Water, RebM) 1 (Water, RebM) 2 (Orange, RebM) 2 (Orange, RebM) Number of measurements 3 3 3 3 3 3 Gas flow rate (mL / min) 150 150 150 150 150 150 Total gas bubbling time (s) 40 40 40 40 40 40 Final foam volume (mL) 114 (SD=3) 120 (SD=1.5) 27 (SD=2.1) 123 (SD=) 125 (SD=1) 20 (SD=1) Final foam conductance (gS) 1.949 2.067 0.194 2,563 2,358 0,208 Total gas volume (mL) 97 97 98 97 97 98 Foam expansion (FE) 5.4 5.1 0 4.1 4.1 0 Foam capacity (FC) 1.18 1.24 0.27 1.27 1.29 0.21 Maximum foam density (MD) 0.184 0.197 - 0.246 0.246 - Volumetric foam stability (s) 114 (SD=17.8) 138 (SD=24.8) 14 (SD=3.8) 171 (SD=17) 181 (SD=6.7) 4 (SD=0) Foam conductance stability (s) 77 52 0 74 78 0
[00137] Table 12 shows that for sample 1, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen. Table 12 shows that for sample 2, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen.
[00138] The results for Protocol 1 (40 s of bubbling air, nitrogen gas and carbon dioxide gas) for samples 3 and 4 are shown in Table 13. Table 13. Gas Ar N2 CO2 Ar N2 CO2 Sample 3 (Water, bubble modifier) 3 (Water, bubble modifier) 3 (Water, bubble modifier) 4 (Orange, bubble modifier) 4 (Orange, bubble modifier) Number of measurements 3 3 3 3 3 3 Gas flow rate (mL / min) 150 150 150 150 150 150 Petition 870210111885, dated 02 / 12 / 2021, pages 62 / 91 / 62 Total gas bubbling time (s) 40 40 40 40 40 40 Final foam volume (mL) 3 (SD=1.7) 4 (SD=1) 5.3 (SD=1.2) 60 (SD=0) 73 (SD=9) 27 (SD=2) Final foam conductance (MS) 0.196 0.196 0.191 6.187 5.582 0.191 Total gas volume (mL) 97 97 98 97 97 98 Foam expansion (FE) 0 0 0 3.3 3.1 0 Foam capacity (FC) 0.03 0.04 0.05 0.85 0.75 0.28 Maximum foam density (MD) - - - 0.31 0.326 - Stability Volumetric foam (s) 1 (SD=0) 1 (SD=0) 1 (SD=1) 17 (SD 6.0) 10 (SD=1.5) 29 (SD 5.9) Foam conductance stability (s) 0 0 0 11 7 0
[00139] Table 13 shows that for sample 4, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen.
[00140] The results for Protocol 1 (40 s of bubbling air, nitrogen gas and carbon dioxide gas) for samples 5 and 6 are shown in Table 14. Table 14. Gas Ar N2 CO2 Ar N2 CO2 Sample 5 (Water, RebM, bubble modifier) 5 (Water, RebM, bubble modifier) 5 (Water, RebM, bubble modifier) 6 (Orange, RebM, bubble modifier) 6 (Orange, RebM, bubble modifier) 6 (Orange, RebM, bubble modifier) Number of measurements 3 3 3 3 3 3 Gas flow rate (mL / min) 150 150 150 150 150 150 Total gas bubbling time (s) 40 40 40 40 40 40 Final foam volume (mL) 117 (SD=2) 116 (SD=4) 35 (SD=0) 119 (SD=4) 124 (SD=3) 34 (SD=1) Final foam conductance (MS) 3.064 2.815 0.796 4.887 5.388 0.328 Total gas volume (mL) 97 97 98 97 97 98 Petition 870210111885, dated 02 / 12 / 2021, pages 63 / 91 / 62 Foam Expansion (FE) 5.3 5.4 0 3.9 3.9 0 Foam Capacity (FC) 1.21 1.20 0.36 1.23 1.28 0.35 Maximum Foam Density (MD) 0.188 0.185 - 0.260 0.257 - Volumetric Foam Stability (s) 137 (SD=15) 135 (SD=14.4) 33 (SD=13) 114 (SD=20.6) 142 (SD=21.4) 18 (SD=6.1) Foam Conductance Stability (s) 51 52 14 59 54 0
[00141] Table 14 shows that for sample 5, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen. Table 14 shows that for sample 6, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen.
[00142] The results for Protocol 1 (40 s of bubbling air, nitrogen gas and carbon dioxide gas) for samples 7 and 8 are shown in Table 15. Table 15. Gas Ar N2 CO2 Ar N2 CO2 Sample 7 (Water, RebM, bubble modifier, preservative) 7 (Water, RebM, bubble modifier, preservative) 7 (Water, RebM, bubble modifier, preservative) 8 (Orange, RebM, bubble modifier, preservative) 8 (Orange, RebM, bubble modifier, preservative) 8 (Orange, RebM, bubble modifier, preservative) Number of measurements 3 3 3 3 3 3 Gas flow rate (mL / min) 150 150 150 150 150 150 Total gas bubbling time (s) 40 40 40 40 40 40 Final foam volume (mL) 109 (SD=4) 119 (SD=1) 36 (SD=1) 44 (SD 5) 41 (SD=3) 15 (SD=1) Final conductance of the foam (gS) 10.463 10.837 1.893 35.737 12.445 0.191 Total gas volume (mL) 97 97 98 97 97 98 Foam expansion (FE) 4.8 4.8 0 3.2 3.4 34.2 Petition 870210111885, dated 02 / 12 / 2021, pages 64 / 91 / 62 Foam capacity (FC) 1.12 1.23 0.37 0.45 0.42 0.16 Maximum foam density (DM) 0.209 0.207 - 0.326 0.292 0.032 Volumetric foam stability (s) 153 (SD=12.7) 164 (SD=11.5) 57 (SD=4) 10 (SD=2.1) 8 (SD=0.6) 4 (SD=0) Foam conductance stability (s) 45 47 13 2 3 0
[00143] Table 15 shows that for sample 7, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen. Table 15 shows that for sample 8, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen.
[00144] The results for Protocol 1 (40 s of bubbling air, nitrogen gas and carbon dioxide gas) for sample 9 are shown in Table 16. Table 16. Gas Ar N2 CO2 Sample 9 (Acid-buffered water, RebM, bubble modifier, preservative) 9 (Acid-buffered water, RebM, bubble modifier, preservative) 9 (Acid-buffered water, RebM, bubble modifier, preservative) Number of measurements 3 3 3 Gas flow rate (mL / min) 150 150 150 Total gas bubbling time (s) 40 40 40 Final foam volume (mL) 74 (SD=2) 75 (SD=3) 32 (SD=3) Final foam conductance (gS) 67.282 70.556 0.614 Total gas volume (mL) 97 97 98 Foam expansion (FE) 3.1 3.1 11 Foam capacity (FC) 0.77 0.77 0.33 Maximum foam density (MD) 0.320 0.327 0.091 Volumetric foam stability (s) 18 (SD=1.2) 18 (SD=1.5) 14 (SD=1.2) Petition 870210111885, dated 02 / 12 / 2021, pages 65 / 91 / 62 Foam conductance stability (s) 9 9 3
[00145] Table 16 shows that for sample 9, bubbling with carbon dioxide gas decreased the final foam volume and final foam capacity compared to bubbling with air or bubbling with nitrogen. Example 8:
[00146] For Example 8, bubble properties were observed by digital photography. Digital photographs of foam bubbles in the respective samples were taken at regular intervals as air-gas bubbling began, throughout the air-gas bubbling, and during the decomposition of the generated foam. Digital photographs were recorded for samples 1, 2, 5, 6, and 7 with air-gas bubbling and nitrogen-gas bubbling. Digital photographs were recorded at 0 s, 15 s, 40 s, 65 s, and 90 s. Figure 5A shows digital photographs of bubbles for sample 1 (Water (RebM)) with air-gas bubbling and nitrogen-gas bubbling at 0 s, 15 s, 40 s, 65 s, and 90 s. Figure 5B shows digital photographs of bubbles for sample 5 (Water (RebM, bubble modifier)) with air gas bubbling and nitrogen gas bubbling at 0 s, 15 s, 40 s, 65 s and 90 s.Figure 5C shows digital bubble photographs for sample 7 (Water (RebM, bubble modifier, preservative)) with air gas bubbling and nitrogen gas bubbling at 0 s, 15 s, 40 s, 65 s and 90 s. Figure 6A shows digital bubble photographs for sample 2 (orange flavor (RebM)) with air gas bubbling and nitrogen gas bubbling at 0 s, 15 s, 40 s, 65 s and 90 s. Figure 6B shows digital bubble photographs for sample 6 (orange flavor (RebM, bubble modifier)) with air gas bubbling and nitrogen gas bubbling at 0 s, 15 s, 40 s, 65 s and 90 s.
[00147] Figure 7A is a graph plotting the average bubble area. Petition 870210111885, dated 02 / 12 / 2021, pp. 66 / 91 / 62 calculated over a 100-second interval for the bubbles in Figures 5 and 6 for samples that were sprayed with air. Figure 7B is a graph plotting the calculated average bubble area over a 100-second interval for the bubbles in Figures 5 and 6 for samples that were sprayed with nitrogen. Figure 7C is a graph plotting the calculated average bubble area over a 100-second interval for the bubbles in Figures 5 and 6 for samples that were sprayed with air and nitrogen. Figure 7B is a graph plotting the calculated average bubble area over a 100-second interval for the bubbles in Figures 5 and 6 for orange-flavored water samples that were sprayed with air and nitrogen. Example 9:
[00148] A model beverage system (carbonated water) was prepared with and without a bubble enhancer. Samples were prepared by dosing a small amount of a concentrated SE solution (1% in non-carbonated water) into plastic serving cups and filling them with carbonated water to achieve final concentrations of 0 to 600 ppm in 100 ppm increments. The comments below are from four staff members familiar with the sensory evaluation of the beverage.
[00149] Carbonated water (0 to 600 ppm): Visual
[00150] a. For systems containing bubble modifier, an increase in the number of bubbles that adhere to the side of the plastic cups.
[00151] b. For systems containing a bubble modifier, a decrease in the size of the bubbles that adhere to the side of the plastic cups.
[00152] c. For systems containing bubble modifier, the bubbles appeared to coalesce more slowly as the concentration of bubble modifier increased.
[00153] d. For systems containing a bubble modifier, smaller bubbles persisted on the walls of the plastic cup for longer. Petition 870210111885, dated 02 / 12 / 2021, pp. 67 / 91 / 62
[00154] e. No perceptible color in solutions at 400 ppm of bubble modifier or less. Flavor
[00155] a. Noticeable increase in the fineness of the buccal sensation of bubbles in systems containing a bubble modifier compared to those that did not include any bubble modifier.
[00156] b. A person observed a slight increase in the perception of acidity at 300 ppm of bubble modifier.
[00157] c. Weak astringency experienced at 500 ppm of bubble modifier.
[00158] d. Mild astringency experienced at 600 ppm of bubble modifier.
[00159] e. A person observed a faint overripe (darkened) fruit flavor at 600 ppm bubble modifier.
[00160] No other botanical flavor perceived at any of the concentrations.
[00161] Figure 8 is a photograph showing, from left to right, samples with 0 ppm, 100 ppm, and 400 ppm of bubble modifier. Petition 870210111885, dated 02 / 12 / 2021, pp. 68 / 91
Claims
1 / 6 CLAIMS 1. A CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE FORMING A FOAM WITH A REDUCED AVERAGE BUBBLE DIAMETER, characterized by comprising: a) steviol glycoside at a concentration of at least 20 ppm, preferably at least 50 ppm; (b) a bubble modifier comprising at least 20% of dicaffeoylquinic acid, including at least one compound selected from the group consisting of 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid, and salts thereof, the bubble modifier present in the steviol glycoside solution at a concentration of 50 ppm to 1600 ppm that is effective in reducing the average bubble diameter in the foam compared to the aqueous solution without the bubble modifier;(ec) dissolved gas to a level that will cause the carbonated aqueous solution to effervesce at 15.6 °C and an ambient air pressure of 1 atmosphere (NTP), wherein the average bubble diameter is measured by the Foamscan test, with an air flow rate of 150 mL / min supplied for 60 seconds to 60 mL of the carbonated aqueous steviol glycoside solution having a temperature of 15.6 °C and determining the average bubble diameter of the bubbles in the foam at a pressure of 1 atmosphere 30 seconds after the gas supply is complete; wherein the carbonated aqueous steviol glycoside solution comprises a ratio of the total concentration of the bubble modifier to the steviol glycoside of between 0.1 and 10; and wherein the bubble modifier comprises less than 0.3% (by weight) of malonate, malonic acid, oxalate, oxalic acid, lactate, lactic acid, succinate, succinic acid, malate, or malic acid;or less than 0.05% (in Petition 870230028868, dated 05 / 04 / 2023, page 8 / 14 2 / 6 weight) of pyruvate, pyruvic acid, fumarate, fumaric acid, tartrate, tartaric acid, sorbate, sorbic acid, acetate or acetic acid; or less than about 0.05% (by weight) of chlorophyll; or less than about 0.1% (by weight) of furans, furan-containing chemicals, theobromine, theophylline or trigonelline as a percentage by weight based on the dry weight of the bubble modifier.
2. Aqueous carbonated solution of steviol glycoside, according to claim 1, characterized in that the concentration of the bubble modifier is from 50 ppm to 600 ppm, from 50 ppm to 500 ppm, from 50 ppm to 400 ppm, from 50 ppm to 300 ppm, from 100 ppm to 600 ppm, from 100 ppm to 500 ppm, from 100 ppm to 400 ppm or from 100 ppm to 300 ppm.
3. Aqueous carbonated solution of steviol glycoside, according to claim 1 or 2, characterized in that the total of all dicaffeoylquinic acids and dicaffeoylquinic salts present in the bubble modifier comprises 25% (by weight) or more, 30% (by weight) or more, 35% (by weight) or more, 40% (by weight) or more, 45% (by weight) or more, 50% (by weight) or more, 60% (by weight) or more, 70% (by weight) or more, 25 to 75% (by weight) or 40 to 60% (by weight) of the total weight of the bubble modifier.
4. A CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, according to any one of claims 1 to 3, characterized in that the bubble modifier comprises a dicaffeoylquinic component that includes at least one compound selected from the group consisting of 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid, and salts thereof; and a monocaffeoylquinic component that includes at least one compound selected from the group consisting of chlorogenic acid, neochlorogenic acid, cryptochlorogenic acid, and salts thereof.
5. Aqueous carbonated solution of steviol glycoside, according to claim 1, characterized by the bubble modifier comprising a dicaffeoylquinic component that includes at least one compound selected from the group consisting of 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid, and salts thereof; and a monocaffeoylquinic component that includes at least one compound selected from the group consisting of chlorogenic acid, neochlorogenic acid, cryptochlorogenic acid, and salts thereof; and wherein the monocaffeoylquinic acid component and the dicaffeoylquinic acid component together comprise more than 50% (by weight), preferably more than 60% (by weight), more than 70% (by weight), more than 80% (by weight), more than 90% (by weight) or more than 95% (by weight) of the bubble modifier.
6. Aqueous carbonated solution of steviol glycoside, according to any one of claims 1 to 5, characterized in that the concentration of steviol glycoside is from 100 ppm to 1600 ppm, preferably from 200 ppm to 1000 ppm, or more preferably from 400 ppm to 800 ppm, and the concentration of bubble modifier is from 50 ppm to 400 ppm, from 50 ppm to 300 ppm, from 100 ppm to 400 ppm, or from 100 ppm to 300 ppm.
7. Aqueous carbonated solution of steviol glycoside, characterized by having an increased foaming capacity or FC30, comprising: a) a steviol glycoside composition comprising at least one of rebaudioside B, rebaudioside D and rebaudioside M, the steviol glycoside composition present in the solution at a concentration of at least 10 ppm, preferably at least 50 ppm or at least 100 ppm;b) a bubble modifier comprising at least 20% of dicaffeoylquinic acid component which includes at least one compound selected from the group consisting of 1,3-dicaffeoylquinic acid, 1,4-dicaffeoylquinic acid, Petition 870230028868, dated 05 / 04 / 2023, page. 10 / 14 4 / 6 1,5-dicaffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid, and salts thereof, the bubble modifier present in the carbonated aqueous solution of steviol glycoside at a concentration of 50 ppm to 1600 ppm, and c) dissolved gas to a level that will cause the carbonated aqueous solution to effervesce at 15.6 °C and an ambient air pressure of 1 atmosphere (NTP), wherein the carbonated aqueous solution of steviol glycoside comprises a ratio of the total concentration of one or more compounds to steviol glycoside between 0.1 and 10;and wherein the bubble modifier and the steviol glycoside are each present in a concentration effective to provide the carbonated aqueous solution of steviol glycoside with a foaming capacity or FC30 of at least 0.8, wherein the FC30 foaming capacity is determined as the volume of foam divided by the volume of air released in the modified carbonated aqueous solution of steviol glycoside in the Foamscan test.
8. Aqueous carbonated solution of steviol glycoside, according to claim 7, characterized in that the bubble modifier and the steviol glycoside are each present in an amount effective to provide a foaming capacity or FC30 of at least 0.9, at least 1.0, at least 1.1, or at least 1.
2.
9. A CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, according to claim 7, characterized in that the bubble modifier comprises 25% (by weight) or more, 30% (by weight) or more, 35% (by weight) or more, 40% (by weight) or more, 45% (by weight) or more, 50% (by weight) or more, 60% (by weight) or more, or 70% (by weight) or more of compounds of the group consisting of dicaffeoylquinic acids and salts thereof, based on a total weight of the bubble modifier.
10. CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, according to claim 7, characterized in that the bubble modifier comprises monocaffeoylquinic acids comprising one or more compounds selected from the group consisting of 3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid and 5-O-caffeoylquinic acid.
11. CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, according to any one of claims 1 to 10, characterized in that the steviol glycoside comprises at least 80% (by weight) of rebaudioside M based on a total weight of steviol glycoside in the sweetened composition.
12. Aqueous carbonated solution of steviol glycoside, according to any one of claims 1 to 11, characterized in that the solution has a steviol glycoside concentration of 100 ppm to 1600 ppm, preferably 200 ppm to 1000 ppm, or more preferably 400 ppm to 800 ppm.
13. CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, according to any one of claims 7 to 12, characterized in that the sweetened composition has a steviol glycoside concentration of 100 ppm to 1600 ppm, preferably 200 ppm to 1000 ppm, or more preferably 400 ppm to 800 ppm, and a bubble modifier concentration of 100 ppm to 1600 ppm, preferably 200 ppm to 1000 ppm, or more preferably 400 ppm to 800 ppm.
14. CARBONATED AQUEOUS SOLUTION OF STEVIOL GLYCOSIDE, according to any one of claims 7 to 13, characterized in that the sweetened composition comprises a ratio of steviol glycoside to bubble modifier of between 1.17 and 2.5, preferably between 1.4 and 2.
15. Aqueous carbonated solution of steviol glycoside, according to any one of claims 1 to 14, characterized in that the solution has a pH of 2 to 4. Petition 870230028868, dated 05 / 04 / 2023, page 12 / 14 6 / 6 16. BEVERAGE COMPRISING THE SOLUTION, as defined in any one of claims 1 to 15, the beverage being characterized by being carbonated with one or more gases selected from the group consisting of air, nitrogen and carbon dioxide.
17. METHOD FOR INCREASING THE VOLUME, VOLUMETRIC STABILITY, FOAMING CAPACITY, FOAM EXPANSION, AND / OR FOAM DENSITY OF A FOAM PRODUCED FROM AN AQUEOUS SOLUTION, the method being characterized by comprising the addition of a bubble modifier and a steviol glycoside to an aqueous solution after, or more desirably before or at the time of gasification of the aqueous solution to prepare a gasified aqueous solution, as defined in any of compositions 1 to 15.
18. BEVERAGE PRODUCT, characterized by comprising a carbonated aqueous solution, as defined in any one of claims 1 to 15.
19. NON-ALCOHOLIC BEVERAGE PRODUCT, characterized by comprising a carbonated aqueous solution, as defined in any one of claims 1 to 15. Petition 870230028868, dated 05 / 04 / 2023, pp. 13 / 14