Emulsion comprising aqueous phase, hop oil, emulsifier and polymeric terpene

Abstract

An emulsion comprising an aqueous phase, an oily phase comprising a hop oil-containing component, an emulsifier, and a polymeric terpene. Use of a polymeric terpene as an osmotic stabilizer for an oil-in-water emulsion. A method for preparing a delivery system for hop oil, the method comprises mixing an aqueous medium, an emulsifier, a polymeric terpene, and an oily phase comprising a hop oil-containing component to form an emulsion.

Description

[0001] EMULSIONS

[0002] TECHNICAL FIELD

[0003] The present disclosure relates to emulsions, in particular hop oil-containing emulsions for flavoring beer and other beverages.

[0004] BACKGROUND

[0005] The following discussion is provided to aid the reader in understanding the disclosure and is not admitted to describe or constitute prior art thereto.

[0006] In order to enhance the flavor and / or aroma of beer and other beverages, a range of hop-oil or hop oil-containing extracts can be added. Hop oil and hop oil-containing extracts have very limited solubilities in water and other solvents, which makes them difficult to use in flavoring compositions or directly in beer or other beverages.

[0007] In order to aid dissolution in beer or other beverages, hop oil can be formulated in a number of ways including the use of a carrier solvent such as propylene glycol or ethanol. Alternatively, hop oil can be suspended as fine droplets in the form of aqueous emulsions. Current products include hop oils or hop oil fractions dissolved in propylene glycol (propane- 1,2-diol, PG) or ethanol; or conventional hop-based emulsions. While the use of propylene glycol is permitted in food products, it is synthetic. Although ethanol is a natural product, it has a high flammability, leading to high transport costs and safety concerns. Conventional hop oil emulsions or hop oilcontaining extract-based emulsions may contain natural ingredients (e.g. xanthan gum, starch) and synthetic food grade emulsifiers, such as polysorbate 80. Although use of these emulsions offers advantages over more traditional practices, such as dry hopping (speedier processing and reduced beer losses), they are susceptible to destabilization due mainly to the Ostwald ripening process, which is the phenomena in which smaller oil droplets diffuse to larger droplets due to a higher Laplace pressure of the small droplets compared to the larger ones.

[0008] Current hop oil emulsions are either unstable over time or contain non-hop derived components. Accordingly, there is a need for hop oil-containing emulsions which are readily dispersible in beer and other beverages, which preferably include only ingredients permitted for traditional beer brewing (e.g., malt, hops, yeast and water), and which exhibit high stability against Ostwald ripening.

[0009] SUMMARY

[0010] In one embodiment, disclosed is an emulsion comprising an aqueous phase, an oily phase comprising a hop oil-containing component, an emulsifier, and a polymeric terpene.

[0011] In another embodiment, disclosed is a use of a polymeric terpene as an osmotic stabilizer for an oil-in-water emulsion.

[0012] In another embodiment, disclosed is a method for preparing a flavouring composition, the method comprises mixing an aqueous medium, an emulsifier, a polymeric terpene, and an oily phase comprising a hop oil-containing component to form an emulsion.

[0013] In another embodiment, disclosed is a method for preparing a delivery system for hop oil, the method comprises mixing an aqueous medium, an emulsifier, a polymeric terpene, and an oily phase comprising a hop oil-containing component to form an emulsion.

[0014] In another embodiment, disclosed is a method of stabilizing an emulsion comprising a hop oil-containing component in a beverage, the method comprising adding an emulsion comprising an aqueous phase, an oily phase comprising a hop oil-containing component, an emulsifier, and a polymeric terpene to a beverage base.

[0015] In another embodiment, disclosed is a method for enriching polymyrcene content in myrcene or hop oil rich in myrcene, the method comprising storing myrcene or the hop oil rich in myrcene for a time and temperature sufficient to polymerize myrcene and / or subjecting myrcene or the hop oil rich in myrcene to distillation.

[0016] These and other features, aspects and advantages of specific embodiments will become evident to those skilled in the art from a reading of the present disclosure. BRIEF DESCRIPTION OF ILLLUSTRATIVE DRAWINGS

[0017] FIGURE l is a graph illustrating emulsions with aged myrcene as oil phase, wherein aging myrcene produces polymyrcene, wherein the fresh droplet size decreases with the age of the myrcene as Ostwald ripening processes are suppressed by the increased polymyrcene content in the oil phase over a period of time.

[0018] FIGURE 2 is a graph illustrating emulsions with aged myrcene as oil phase, wherein the droplet size of distilled myrcene condensate (no polymyrcene) is larger and increases over a period of time, as compared to the smaller droplet size of distilled myrcene residue (containing polymyrcene) which remains stable over a period of time.

[0019] FIGURE 3 is a graph illustrating emulsions with distilled myrcene as oil phase, wherein the droplet size of distilled myrcene condensate (no polymyrcene or other osmotic stabilizer) is larger and increases over a period of time, as compared to the smaller droplet size of myrcene in an emulsion containing 4% MCT (osmotic stabilizer) which remains stable over a period of time.

[0020] FIGURE 4 is a graph illustrating that the more polymyrcene present in the samples the more stable the droplet size. In particular, Oil Y contains a higher polymyrcene content than Oil X, and therefore Oil Y is better stabilized against droplet growth by Ostwald ripening as no increase in droplet size over time can be observed.

[0021] DETAILED DESCRIPTION

[0022] Before further describing various embodiments of the present disclosure in more detail by way of exemplary description, examples, and results, it is to be understood that the compounds, compositions, and methods of the present disclosure are not limited in application to the details of specific embodiments and examples as set forth in the description set forth herein. The description provided herein is intended for purposes of illustration only and is not intended to be construed in a limiting sense. As such, the language used herein is intended to be given the broadest possible scope and meaning, and the embodiments and examples are meant to be exemplary, not exhaustive. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description only and should not be regarded as limiting unless otherwise indicated as so. Moreover, in the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the present disclosure. However, it will be apparent to a person having ordinary skill in the art that the present disclosure may be practiced without these specific details. In other instances, features which are well known to persons of ordinary skill in the art have not been described in detail to avoid unnecessary complication of the description. It is intended that all alternatives, substitutions, modifications, and equivalents apparent to those having ordinary skill in the art are included within the scope of the present disclosure. Thus, while the compounds, compositions, and methods of the present disclosure have been described in terms of particular embodiments, it will be apparent to those of skill in the art that variations may be applied to the compounds, compositions, and methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit, and scope of the inventive concepts.

[0023] As a result of the inventors’ research, it has been found that polymeric terpenes, such as polymyrcene, can be used to stabilize oil-in-water emulsions. In particular, it has been found that polymeric terpenes are capable of producing smaller and more stable oil droplets in oil-in-water emulsions, as compared to the same emulsion but without polymeric terpenes. It has also been found that the more polymeric terpenes present in oil-in-water emulsions, the smaller and more stable the oil droplet size.

[0024] The presently disclosed emulsion technology is effective in finely dispersing hop oils and has the following additional advantages: i) Readily dispersible in aqueous mediums; ii) Reduction or elimination of solvents, such as ethanol and propylene glycol; iii) Elimination of artificial osmotic stabilizers; iv) Suitable for wide variety of hop oils; v) Suitable for use in beer and beer-type beverage flavor formulations. According to some embodiments, disclosed is an emulsion comprising an aqueous phase, an oily phase comprising a hop oil-containing component, an emulsifier, and a polymeric terpene. Surprisingly and unexpectedly, it has been found that such a combination of constituents provides excellent flavoring, is readily dispersible in beer and other beverages, and is stable against the Ostwald ripening process.

[0025] An emulsifier adsorbs to the interface between oil, such as hop oil, and water and reduces the interfacial energy in the system thereby enabling droplet break up as well as droplet stabilization. Emulsifiers create an interfacial layer that hinders droplets from getting so close that they coalesce. In certain embodiments, the emulsifier comprises a hop-derived emulsifier. In some cases, the hop-derived emulsifier comprises an aqueous hop extract. In some cases, the hop- derived emulsifier comprises a polar hop extract.

[0026] The hop-derived emulsifier may comprise a hop acid. As used in the present specification, "a" or "an" is employed to describe components, elements, features and method / process steps of various illustrative embodiments disclosed herein. The use of “a” or “an” should be interpreted to include one or more than one. In some embodiments, the hop acid is selected from the group consisting of hop beta acids (e.g., lupulones), hop alpha acids (e.g., humulones), iso-alpha acid, rho-iso-alpha acid, tetrahydro-iso-alpha acid, hexahydro-iso-alpha acid, hexahydro-iso-beta acid, hulupone, humulinone, and combinations thereof.

[0027] In some cases, the hop-derived emulsifier is substantially free of alpha-acids. As used herein, the phrase “substantially free of alpha-acids” refers to a composition having less than 5% alpha acids, or less than 4% alpha acids, or less than 3% alpha acids, or less than 2% alpha acids, or less than 1% alpha acids, based on the total weight of the hop-derived emulsifier.

[0028] In some embodiments, the hop-derived emulsifier comprises about 20% to about 70% beta acids, or about 25% to about 65% beta acids, or about 30% to about 55% beta acids, based on the total weight of the hop-derived emulsifier. In some embodiments, the hop-derived emulsifier comprises less than 2% alpha acids and about 30% to about 55% beta acids, based on the total weight of the hop-derived emulsifier. In the present disclosure, the term “about” used in connection with a value is inclusive of the stated value and has the meaning dictated by the context. For example, it includes at least the degree of error associated with the measurement of the particular value. One of ordinary skill in the art would understand the term “about” is used herein to mean that an amount of “about” of a recited value produces the desired degree of effectiveness in the compositions and / or methods of the present disclosure. One of ordinary skill in the art would further understand that the metes and bounds of “about” with respect to the value of a percentage, amount or quantity of any component in an embodiment can be determined by varying the value, determining the effectiveness of the compositions for each value, and determining the range of values that produce compositions with the desired degree of effectiveness in accordance with the present disclosure.

[0029] It should be understood that when a range of values is described in the present disclosure, it is intended that any and every value within the range, including the end points, is to be considered as having been disclosed. For example, “a range of from 50 to 100” of a component is to be read as indicating each and every possible number along the continuum between 50 and 100. It is to be understood that the inventors appreciate and understand that any and all values within the range are to be considered to have been specified, and that the inventors have possession of the entire range and all the values within the range.

[0030] In some embodiments, the hop-derived emulsifier is a CO2 extract, typically from a liquid (subcritical) CO2 extraction or supercritical CO2 extraction, an oil-enriched CO2 extract, or fractions thereof.

[0031] In some embodiments, the hop-derived emulsifier is obtained by or obtainable from extracting hops or spent hops with water, preferably with hot water, optionally with boiling water. Alternatively, the extract of hops is a de-solventised extract obtained by or obtainable from an ethanolic hop extraction process.

[0032] As used in the present specification, any of the terms “illustratively,” "preferably," "commonly," and "typically" are not intended to, and do not, limit the scope of the claimed embodiments, or to imply that certain features are critical, essential, important, or required to the structure or function of the claimed processes and resulting emulsion. Rather, these terms are merely intended to identify particular aspects of an embodiment or to emphasize alternative or additional features that may or may not be utilized in a particular embodiment.

[0033] In some embodiments, the hop-derived emulsifier comprises 10% w / w or less, or 8% w / w or less, or 6% w / w or less, or 5% w / w or less water.

[0034] As used in the present specification, the term "or" refers to an inclusive “or” and not to an exclusive “or”. For example, the phrase “A or B” is satisfied by any one of the following: A is present and B is not present, A is not present and B is present, and both A and B are present.

[0035] The emulsion further comprises a hop oil-containing component. In some cases, the hop oil-containing component comprises a hop oil, an oil-rich hop extract, or combinations thereof. According to certain embodiments, the oil-rich hop extract is a CO2 extract or an ethanolic extract.

[0036] The hop oil-containing component can be any flavor or aroma-providing hop extract as would be used by a brewer. For example, the hop oil-containing component can be the product of processes such as steam distillation, CO2 or ethanol extraction, and may be followed by distillation or a combination of processes. The hop oil-containing component may essentially be a substantially pure mixture of hop oils or an extract containing hop oils, which may be concentrated extracts or fractions of hop oils.

[0037] Traditionally, hop oil itself is added during the brewing process in a small amount, for example, about 1 ppm to about 5 ppm, i.e. 0.1 ml per hectoliter which is approximately 0.1-0.5 ml of hop oil per barrel of beer (BBL). When adding the oil alone, there is a high chance that the oil will coalesce on the sides of the tank or block a valve. The oil has a lower density than the brew / water, resulting in hot pockets of oil and / or oil slicks and ringing.

[0038] Accordingly, breweries currently using hop oil have created additional processing steps and need, in most cases, additional processing equipment to infuse the hop oil into their production process. Extra steps and equipment are required when standalone hop oil is used to improve hop additions. Examples of additional steps can include diluting hop oil with high proof ethanol and mixing for up to 12 hours on a stir plate, as well as a hop gun procedure during which a hop gun is filled and circulated for approximately 1 hour at a particular flow rate. Additional equipment can include hop injection equipment, such as a hop whirlpool addition, hop back, or hop infusers.

[0039] The disclosed emulsion allows for seamless integration. One simply measures out the required volume and then adds the emulsion directly to the tank or barrel of beer, or other beverage. No special processing or special equipment is required. The disclosed emulsion evenly distributes oil droplets of the hop oil throughout water for use in beer or other beverages. During the emulsification, an emulsifier enrobes the oil droplets for use in beer without losing any of the beer product to absorption by traditional hops.

[0040] The disclosed emulsion further comprises a polymeric terpene. In certain embodiments, the polymeric terpene comprises a polymer having myrcene subunits, pinene subunits, limonene subunits, farnesene subunits, phellandrene subunits and / or ocimene subunits, including any isomers thereof. The pinene subunits may comprise, without limitation, alpha-pinene, beta-pinene or combinations thereof. The phellandrene subunits may comprise, without limitation, alphaphellandrene, beta-phellandrene or combinations thereof. The farnesene subunits may comprise, without limitation, alpha-farnesene, beta-famesene, and / or any corresponding stereoisomers. The ocimene subunits may comprise, without limitation, allo-ocimene.

[0041] According to certain illustrative embodiments, the polymeric terpene is an intentional addition to the emulsion. The phrase “intentional addition” refers to polymeric terpene that is intentionally added to the disclosed emulsion, rather than polymeric terpene that may be formed over a period of time from monoterpene subunits. The inclusion of an intentional addition of polymeric terpene results in an emulsion that advantageously exhibits high stability against Ostwald ripening. In this context, the term “high stability” refers to hop oil droplets having an average diameter of about 300 nm or less, or about 250 nm or less, or about 200 nm or less after being stored for a period of at least 20 weeks at about 4°C.

[0042] In some embodiments, the polymeric terpene comprises a polymer having myrcene subunits, pinene subunits, limonene subunits, farnesene subunits, phellandrene subunits and / or ocimene subunits with an average molecular weight greater than about 10,000 g / mol, or greater than about 11,000 g / mol, or greater than about 12,000 g / mol. or greater than about 13,000 g / mol, or greater than about 14,000 g / mol, or greater than about 15,000 g / mol. The polymeric terpene may be obtained by polymerizing myrcene, pinene, limonene, famesene, phellandrene and / or ocimene. In certain embodiments, the polymeric terpene is derived from hops.

[0043] An osmotic stabilizer reduces or stops Ostwald-ripening. Especially for oil phases with a rest solubility in water like some flavor oils (e.g. limonene, myrcene) it is important to stop the diffusion from small droplets to larger droplets that is occurring due to a higher Laplace pressure on the small droplets compared to the larger ones. The solubility of the flavor in the water phase around the small droplets increases due to the higher pressure and diffusion from smaller to larger droplets occurs to balance the differences in concentration. This effect is known as Ostwald- ripening. It has been found that the inclusion of a polymeric terpene in combination with the other constituents of the disclosed emulsion creates an osmotic pressure that is counteracting the Laplace pressure difference, resulting in an emulsion that exhibits high stability against Ostwald ripening. A typical osmotic agent used in the flavor industry is medium chain triglycerides (MCT). However, MCT or a vegetable oil would render the emulsion no longer hop derived.

[0044] According to certain embodiments, the emulsion comprises from about 0.1 % w / w to about 30% w / w, or from about 0.5 % w / w to about 15% w / w, or from about 1 % w / w to about 5% w / w of an emulsifier.

[0045] According to certain embodiments, the emulsion comprises from about 0.1 % w / w to about 50% w / w, or from about 1% w / w to about 20% w / w, or from about 5 % w / w to about 15% w / w of a hop oil-containing component.

[0046] According to certain embodiments, the emulsion comprises from about 0.1 % w / w to about 10% w / w, or from about 0.5 % w / w to about 5% w / w, or from about 1 % w / w to about 5% w / w of a polymeric terpene.

[0047] According to certain embodiments, the emulsion comprises from about 0 % w / w to about 95% w / w, or from about 10 % w / w to about 90% w / w, or from about 70 % w / w to about 90% w / w of water. According to certain embodiments, the emulsion comprises from about 60% w / w to about 80% w / w glycerin. In some cases, the emulsion comprises from about 65% w / w to about 77% w / w glycerin. At these concentrations, the glycerin reduces the water activity to below 0.6 which leads to a microbiologically stable product. In certain embodiments, the emulsion is substantially free of glycerin. As used herein, the phrase “substantially free of glycerin” refers to an emulsion having less than 5% glycerin, or less than 4% glycerin, or less than 3% glycerin, or less than 2% glycerin, or less than 1% glycerin, or 0% glycerin, based on the total weight of the emulsion.

[0048] As used in this specification, the terms "comprises," "comprising," “contains,” “containing,” "includes," "including," "has," or "having," are all open-ended expressions and are intended to cover apparatus, compositions, methods, processes, products, or systems that comprise a recited list of components, elements, and features, and any and all additional components, elements and features that are not expressly recited.

[0049] In some cases, the emulsion comprises only ingredients permitted for traditional beer brewing, which may refer to beer produced in accordance with the German Beer Purity Law (e.g., malt, hops, yeast and water). In certain embodiments, the emulsion consists of, or consists essentially of, hop derived ingredients and water. When used herein “consisting of’ excludes any element, step, or ingredient not specified in the aspect, embodiment and / or claim element. When used herein, “consisting essentially of’ does not exclude materials or steps that do not materially affect the basic and novel characteristics of the aspect, embodiment and / or claim.

[0050] The term “beer” is used in this application in its broadest sense of encompassing all styles of beer, namely a beverage brewed, most usually, from cereal grains such as barley, wheat, maize or corn, although other ingredients are used in other traditional beers around the world. The present invention is concerned with adding a stable hop flavor and / or aroma emulsion to any product to which it is desired to add or enhance hop flavor or aroma. The present emulsion may be included in any type of beverage, such as beer, non-alcoholic beer, beer-type beverages, carbonated soft drinks, and the like. In some cases, the emulsion is substantially free of one or more of: MCT, vegetable oils and fats (e.g. from sunflower seeds, coconut, rapeseed, olive, safflower, palm, cocoa butter, grape seed, pumpkin seed), nut oils (e.g. peanut, walnut, almond, hazelnut), animal fats, glycerol ester of gum rosin, glycerol ester of wood rosin, sucrose acetate isobutyrate, and waxes (e.g. bee, carnauba, candelila, citrus peel). In accordance with this embodiment, the phrase “substantially free” refers to an emulsion containing less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1%, or 0% of any of the above mentioned compounds, based on the total weight of the emulsion.

[0051] According to certain embodiments, the emulsion is free of, or substantially free of, nonhop derived ingredients. In accordance with this embodiment, the phrase “substantially free” refers to an emulsion containing less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1% of non-hop derived ingredients, based on the total weight of the emulsion.

[0052] In some aspects, the emulsion is stabilized against Ostwald-ripening and exhibits no, or essentially no, increase in droplet size over time. In accordance with this embodiment, the phrase “essentially no” refers to an increase in droplet size of less than 20%, or less than 15%, or less than 10% after being stored for a period of at least 20 weeks at about 20°C.

[0053] In certain embodiments, the disclosed emulsion is stable after being stored for a period of at least 20 weeks at about 4°C. In further embodiments, the emulsion is stable after being stored for a period of at least 20 weeks at about 20°C. In this context, the term “stable” refers to hop oil droplets having an average diameter of about 300 nm or less, or about 250 nm or less, or about 200 nm or less after being stored for a period of at least 20 weeks at about 4°C or at about 20°C.

[0054] In some cases, the emulsion comprises hop oil droplets having an average diameter of about 300 nm or less, or about 250 nm or less, or about 200 nm or less after being stored for a period of at least 20 weeks at about 4°C.

[0055] Also disclosed is use of a polymeric terpene as an osmotic stabilizer for an oil-in-water emulsion. Also disclosed is use of polymyrcene as an osmotic stabilizer for an emulsion comprising a hop oil-containing component.

[0056] Also disclosed is a method for preparing a flavoring composition, the method comprises mixing an aqueous medium, an emulsifier, a polymeric terpene, and an oily phase comprising a hop oil-containing component to form an emulsion. In certain embodiments, the disclosed emulsion is prepared via homogenization processes, such as high-pressure homogenization (HPH), which involves using a high-pressure pump to force fluid through a small orifice.

[0057] Also disclosed is a method for preparing a delivery system for hop oil, the method comprises mixing an aqueous medium, an emulsifier, a polymeric terpene, and an oily phase comprising a hop oil-containing component to form an emulsion.

[0058] Also disclosed is a method of stabilizing an emulsion comprising a hop oil-containing component in a beverage, the method comprising adding the disclosed emulsion to a beverage base. In some cases, the beverage is a beer or beer-type beverage. In certain embodiments, the emulsion is added to the wort, the cooled wort, at the start of, during or after fermentation or maturation or after final filtration. Advantageously, the emulsion may be derived exclusively from hops to replicate the “dry hopping” process during brewing. Preparing emulsions that are stable against the Ostwald ripening process using only hop derived ingredients becomes possible based on the present invention.

[0059] Also disclosed is a method of intentionally enriching polymyrcene content in myrcene or the hop oil rich in myrcene, the method comprises storing myrcene or the hop oil rich in myrcene for a time and temperature sufficient to polymerize myrcene and / or subjecting myrcene or the hop oil rich in myrcene to distillation. In certain embodiments, the myrcene or the hop oil rich in myrcene is stored for 2 weeks, or 3 weeks, or 4 weeks, or 5 weeks, or 6 weeks, or 7 weeks, or 8 weeks, or 10 weeks, or 11 weeks, or 12 weeks at approximately 4°C or approximately 20°C. EXAMPLES

[0060] The following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present disclosure, as many variations of the invention are possible without departing from the spirit and scope of the present disclosure.

[0061] Example 1 - Emulsions with aged myrcene as oil phase

[0062] An emulsion comprising an emulsifier (quillaja) and myrcene was prepared (Example 1 A).

[0063] A fresh emulsion comprising quillaja and aged myrcene was also prepared (Example 1B- 1H).

[0064] The myrcene was aged over a period of 11 weeks at 4°C. A fresh emulsion was prepared with the aged myrcene at each timepoint of 1, 2, 3, 4, 6, 8 and 11 weeks. The stability of the emulsions in accordance with Examples 1A-1H were evaluated by storing the emulsions for 1 week at 4°C.

[0065] Aging myrcene produces polymyrcene. This data correlates well with the emulsification results: the more polymyrcene present in the samples the smaller and more stable the droplet size. As depicted in the graph according to Figure 1, it is evident that the oil droplet size in the Examples decreases with the age of the myrcene used to make the emulsion as the diffusion processes that happen already within seconds and minutes after the emulsion preparation (before the first droplet size measurement) are suppressed by the polymyrcene in the oil phase. Also, it is evident that the stability is increased as longer-term diffusion processes are stopped.

[0066] Example 2 - Polymeric Terpene Improving Stability of Emulsion

[0067] An emulsion comprising an emulsifier (quillaja) and freshly distilled myrcene condensate (no polymyrcene) (Example 2A) was prepared. An emulsion comprising quillaja and distilled myrcene residue (13% of polymyrcene (PM)) (Example 2B) was also prepared. Both samples were stored for 21 weeks at 4°C. The oil droplets in the emulsion without polymyrcene (Example 2A) had an initial diameter of approximately 250 nm, which increased to about 280 nm at 7 weeks, and further increased to about 360 nm at 21 weeks. In contrast, the oil droplets in the emulsion containing polymyrcene (Example 2B) had an initial diameter of approximately 160 nm, and exhibited very minor increases to about 170 nm at 7 weeks and 190 nm at 21 weeks. As evident from the graph according to Figure 2, the emulsion containing polymyrcene (Example 2B) contained smaller and more stable droplets, as compared to the emulsion without polymyrcene (Example 2A).

[0068] Example 3 - Adding MCT as Osmotic Stabilizer

[0069] An emulsion comprising an emulsifier (quillaja) and freshly distilled myrcene condensate (no polymyrcene) (Example 3 A) was prepared. An emulsion comprising quillaja, freshly distilled myrcene and 4% MCT (typical osmotic agent used in the flavor industry) (Example 3B) was also prepared. Both samples were stored for 8 weeks at 4°C. The oil droplets in the emulsion without polymyrcene (Example 3A) had an initial diameter of approximately 250 nm, which increased to about 280 nm at 7 weeks. In contrast, the oil droplets in the emulsion containing MCT (Example 3B) had an initial diameter of approximately 160 nm and maintained a similar diameter for at least 7 weeks. As evident from the graph according to Figure 3, the emulsion containing MCT (Example 3B) contained smaller and more stable droplets, as compared to the emulsion without polymyrcene (Example 3 A). These results show that polymeric terpenes exhibit substantially the same function as non-hop derived osmotic agents.

[0070] Example 4 - Changes to Viscosity and Refractive Index with Myrcene over 11 weeks at 40°C

[0071] In the following table, the evolution of viscosity and Refractive Index (“RI”) with aging time at 40°C is shown: As shown by Runckel, W. and L. Goldblatt, “Inhibition of myrcene polymerization during storage”, Industrial & Engineering Chemistry, 1946, 38(7): p. 749-751, which is hereby incorporated by reference in its entirety, the change of refractive index and viscosity can be attributed to the increased polymer content.

[0072] This data is also supported by the measurement of the polymer by Size Exclusion Chromatography (SEC) which separates molecules based on their size by filtration through a gel. The gel consists of spherical beads containing pores of a specific size distribution. Separation occurs when molecules of different sizes are included or excluded from the pores within the matrix. Small molecules diffuse into the pores and their flow through the column is retarded according to their size, while large molecules do not enter the pores and are eluted in the column's void volume. Consequently, molecules are separated based on their size as they pass through the column and are eluted in order of decreasing molecular weight (MW).

[0073] This data correlates well with the emulsification results: the more polymyrcene present in the samples the smaller and more stable the droplet size.

[0074] Example 5 - Preparing polymyrcene

[0075] Various chemical methods can be used for the generation of polymyrcene. In addition, storing myrcene at an elevated temperature can also produce polymyrcene. Applicant has found that distillation of hop oils or hop extracts can also increase the ratio of polymyrcene to myrcene. The below table shows enrichment of polymyrcene content from a sample of myrcene by distillation. Example 6 - Influence of the Intrinsic Polymyrcene Content in Hop Oil with Different Emulsifiers

[0076] Emulsions were prepared comprising a hop oil “X” (9 % myrcene, viscosity r] (at 10 1 / s) = 7.4 mPa*s) and a hop oil “Y” (70 % myrcene, viscosity r] (at 10 l / s= 363.1 mPa*s ). High viscosity and high myrcene content correlate to high polymyrcene content, thus Oil “X” has lower polymyrcene content than “Y”.

[0077] An emulsion comprising an emulsifier (quillaja) and hop oil “X” was prepared (Example 6 A). An emulsion comprising an emulsifier (quillaja) and hop oil “Y” was also prepared (Example 6B).

[0078] The viscosity of Oil “Y” was too high for ideal droplet break-up and the initial droplet size is slightly larger, as shown in Figure 4, but it can be seen that oil “Y” is better stabilized against droplet growth by Ostwald ripening as no increase in droplet size over time can be observed, while Oil “X” with the lower polymyrcene (“PM”) content is not stable (see Figure 4, droplet size of Oil “X” increases over time).

[0079] Volatile composition of hop oils “X” and “Y”

[0080] The higher concentration of myrcene and dimyrcenes indicates the presence of non-volatile polymyrcene in the sample which is confirmed by SEC.

[0081] An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil “X”, 75% glycerin, and 12.5% water was prepared (Example 6C). An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil “Y”, 75% glycerin, and 12.5% water was prepared (Example 6D).

[0082] An emulsion comprising 1.25% hop derived emulsifier, 10% hops oil “X”, 76.25% glycerin, and 12.5% water was prepared (Example 6E). An emulsion comprising 1.25% hop derived emulsifier, 10% hops oil ”Y”, 76.25% glycerin, and 12.5% water was prepared (Example 6F).

[0083] As evident from the above results, an emulsion containing hop oil having a low polymyrcene content (Example 6A) is not stable, whereas the same emulsion containing hop oil having a high polymyrcene content (Example 6B) is stable. Examples 8C-8D demonstrate the same effect with a different hop derived emulsifier. Examples 8E-8F demonstrate the same effect with a different emulsifier concentration. Example 7 - Osmotic Agent is Needed to Stabilize Hop Oil Emulsions

[0084] An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil, 75% glycerin, and 12.5% water was prepared (Example 7A). An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil, 71% glycerin, 12.5% water, and 4% MCT was prepared (Example 7B). An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil, and 87.5% water was prepared (Example 7C). An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil, and 83.5% water was prepared (Example 7D).

[0085] As evident from the above results, the hop oil emulsion emulsified with hop derived emulsifier (beta acids) is not stable without the addition of an osmotic agent, in this case MCT. Glycerin is added to ensure microbiological stability of Examples 7A and 7B.

[0086] Examples 7C and 7D exhibited the same effect as Examples 7A and 7B, but no glycerin is added. Example 7C only contained beer ingredients but is not stable. Examples 7D with the additional MCT does not show an increase of the droplet size over time. This shows an osmotic agent is needed.

[0087] Example 8 - Influence of Polymerized Myrcene on Emulsions with Hop Emulsifiers

[0088] An emulsion comprising 1.25% hop derived emulsifier, 10% hops oil “X” (low in polymyrcene), 76.25% glycerin, and 12.5% water was prepared (Example 8A). An emulsion comprising 1.25% hop derived emulsifier, 10% hops oil “X” (low in polymyrcene), 76.25% glycerin, 12.5% water and 1% polymerized myrcene (aged at 40°C for 11 weeks) was prepared (Example 8B). The droplet size of Example 8 A, which contains a hop derived emulsifier and 10% of a hop oil low in polymyrcene, increases over time. When 1% of polymerized myrcene is added to the sample (Example 8B), the initial droplet size decreases and the stability over time improves distinctly. Glycerin was used as a solvent to improve microbiological stability of the samples, but glycerin can be replaced with water while achieving the same or similar effect.

[0089] Example 9 - Hop Oils can be Mixed to Adjust Polymyrcene Content

[0090] An emulsion comprising 1.25% hop derived emulsifier, 10% hops oil “X” (low in polymyrcene), and 88.75% water was prepared (Example 9A). An emulsion comprising 1.25% hop derived emulsifier, 10% hops oil “X” (low in polymyrcene), 1% hops oil “Y” (high in polymyrcene), and 88.75% water was prepared (Example 9B).

[0091] The addition of 1% of the hop oil rich in polymyrcene leads already to more stable droplets.

[0092] Example 10 -Emulsions produced with high pressure homogenization

[0093] An emulsion comprising 2.5% hop derived emulsifier, 10% hops oil “X” (low in polymyrcene), 1% MCT, 74% glycerin, and 12.5% water was prepared (Example 10A). An emulsion comprising 2.5% hop derived emulsifier, 5% hops oil “Y” (high in polymyrcene), 80% glycerin, and 12.5% water was prepared (Example 10B). Both examples were processed via pre-homogenization with a tooth rimmed dispersion machine (Polytron 6000 at a revolution of 15.000 rpm for 2 min) and then high pressure homogenization (“HPH”) (GEA lab homogenizer PandaPlus 2000) for 3 passes at a pressure drop of Ap= 350 / 50 bar. Except for glycerin, Example 10B only contains beer approved ingredients (i.e., water and hop-derived ingredients). Glycerin was used as a solvent to improve microbiological stability of the samples, but glycerin can be replaced with water while achieving the same or similar effect.

Claims

What is claimed is:

1. An emulsion comprising an aqueous phase, an oily phase comprising a hop oil-containing component, an emulsifier, and a polymeric terpene.

2. The emulsion of claim 1, wherein the emulsifier comprises a hop-derived emulsifier.

3. The emulsion of claim 2, wherein the hop-derived emulsifier comprises a hop acid.

4. The emulsion of claim 3, wherein the hop acid is selected from the group consisting of hop beta acids, hop alpha acids, iso-alpha acid, rho-iso-alpha acid, tetrahydro-iso-alpha acid, hexahydro-iso-alpha acid, hexahydro-iso-beta acid, hulupone, lupulone, humulone, humulinone, and combinations thereof.

5. The emulsion of claim 2, wherein the hop-derived emulsifier is substantially free of alphaacids.

6. The emulsion of claim 2, wherein the hop-derived emulsifier comprises less than 2% alpha acids and 30% to 55% beta acids, based on the total weight of the hop-derived emulsifier.

7. The emulsion of claim 2, wherein the hop-derived emulsifier comprises an aqueous hop extract.

8. The emulsion of claim 1, wherein the polymeric terpene comprises a polymer having myrcene subunits.

9. The emulsion of claim 1, wherein the polymeric terpene comprises a polymer having myrcene subunits with an average molecular weight greater than 10,000 g / mol.

10. The emulsion of claim 1, wherein the polymeric terpene is obtained by polymerizing myrcene.

11. The emulsion of claim 1, wherein the polymeric terpene is derived from hops.

12. The emulsion of claim 1, wherein the hop oil-containing component comprises a hop oil, an oil-rich hop extract, or combinations thereof.

13. The emulsion of claim 11, wherein the oil-rich hop extract is a CO2 extract or an ethanolic extract.

14. The emulsion of claim 1, wherein the emulsion is substantially free of MCT.

15. The emulsion of claim 1, wherein the emulsion is substantially free of non-hop-derived ingredients.

16. Use of polymyrcene as an osmotic stabilizer for an emulsion comprising a hop oil-containing component.

17. A method for preparing a flavouring composition, the method comprises mixing an aqueous medium, an emulsifier, a polymeric terpene, and an oily phase comprising a hop oil-containing component to form an emulsion.

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