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Title:
CHEWING GUM COMPOSITIONS HAVING CONTROLLED RELEASE OF COOLING AGENTS AND METHODS OF MANUFACTURE
Document Type and Number:
WIPO Patent Application WO/2017/105634
Kind Code:
A1
Abstract:
A chewing gum composition includes a water insoluble gum base phase and a water soluble phase. The water insoluble gum base phase includes a gum base composition and a first cooling agent including N-ethyl-2,2-diisopropylbutanamide. The water soluble phase includes a second cooling agent including ethyl 3-(p-menthane-3-carboxamido)acetate and N,2,3-trimethyl-2-isopropyl butanamide. A method of making a chewing gum composition having improved cooling is also disclosed. The method includes mixing a first cooling agent with a gum base composition to provide a gum base phase including N-ethyl-2,2-diisopropylbutanamide, and combining a water soluble phase with the gum base phase to provide the chewing gum composition. The water soluble phase includes a second cooling agent including ethyl 3-(p-menthane-3-carboxamido)acetate and N,2,3-trimethyl-2-isopropyl butanamide.

Inventors:
LUO, Shiuh (100 Deforest Avenue, East Hanover, New Jersey, 07936, US)
Application Number:
US2016/058644
Publication Date:
June 22, 2017
Filing Date:
October 25, 2016
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
INTERCONTINENTAL GREAT BRANDS LLC (100 Deforest Avenue, East Hanover, New Jersey, 07936, US)
International Classes:
A23L27/20; A23G4/06; A23G4/08
Domestic Patent References:
WO2011163152A12011-12-29
WO2011159927A12011-12-22
WO2000033664A12000-06-15
Foreign References:
US20110159141A12011-06-30
US5415880A1995-05-16
US7923577B22011-04-12
US20110070171A12011-03-24
US20110070329A12011-03-24
US4279931A1981-07-21
US4619834A1986-10-28
US3492131A1970-01-27
Attorney, Agent or Firm:
PAGE, Samantha M. (Cantor Colburn LLP, 20 Church Street22nd Floo, Hartford Connecticut, 06103, US)
Download PDF:
Claims:
CLAIMS

1. A chewing gum composition comprising,

a water insoluble gum base phase comprising a gum base composition and a first cooling agent comprising 0.01 to 1 weight percent N-ethyl-2,2-diisopropylbutanamide; and a water soluble phase comprising a second cooling agent comprising,

0.005 to 0.3 weight percent ethyl 3-(p-menthane-3-carboxamido)acetate; and 0.005 to 0.3 weight percent N,2,3 rimethyl-2-isopropyl butanamide.

2. The chewing gum composition of claim 1 , wherein

the first cooling agent comprises 0.1 to 0.5 weight percent N-ethyl-2,2- diisopropylbutanamide; and

the second cooling agent comprises 0.01 to 0.1 weight percent ethyl 3-(p-menthane-3- carboxamido)acetate and 0.0075 to 0.15 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

3. The chewing gum composition of claim 1 or 2, wherein

the first cooling agent comprises 0.20 to 0.25 weight percent of N-ethyl-2,2- diisopropylbutanamide; and

the second cooling agent comprises 0.025 to 0.035 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate and 0.0075 to 0.0125 weight percent N,2,3-trimethyl-2- isopropyl butanamide.

4. The chewing gum composition of any one of claims 1 to 3. wherein the water soluble phase further comprises a fruit flavor, a mint flavor, or a combination thereof.

5. The chewing gum composition of any one of claims 1 to 4, wherein the water soluble phase further comprises a fruit flavor comprising watermelon flavor, strawberry flavor, banana flavor, mango flavor, blueberry flavor, or a combination thereof.

6. The chewing gum composition of any one of claims 1 to 5, further comprising 0 to 2 weight percent menthol.

7. The chewing gum composition of any one of claims 1 to 6, wherein the first cooling agent and the second cooling agent are not encapsulated.

8. A method of making a chewing gum composition having improved cooling, the method comprising,

mixing a first cooling agent with a gum base composition to provide a gum base phase comprising 0.01 to 1 weight percent N-ethyl-2,2-diisopropylbutanamide; and

combining a water soluble phase with the gum base phase to provide the chewing gnm composition, wherein the water soluble phase comprises a second cooling agent comprising,

0.005 to 0.3 weight percent ethyl 3-(p-menthane-3-carboxamido)acetate; and 0.005 to 0.3 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

9. The method of claim 8, wherein

the first cooling agent comprises 0.1 to 0.5 weight percent N-ethyl-2,2- diisopropylbutanamide; and

the second cooling agent comprises 0.01 to 0.1 weight percent ethyl 3-(p-menthane-3- carboxamido)acetate and 0.0075 to 0.15 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

10. The method of claim 8 or 9, wherein

the first cooling agent comprises 0.20 to 0.25 weight percent of N-ethyl-2,2- diisopropylbutanamide; and

the second cooling agent comprises 0.025 to 0.035 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate and 0.0075 to 0.0125 weight percent N,2,3-trimethyl-2- isopropyl butanamide.

1 1. The method of any one of claims 8 to 10, wrherein the water soluble phase further comprises a fruit flavor, a mint flavor, or a combination thereof.

12. The method of any one of claims 8 to 1 1, wherein the w¾ter soluble phase further comprises a watermelon flavor, strawberry flavor, banana flavor, mango flavor, blueberry flavor, or a combination thereof.

13. The method of any one of claims 8 to 12, further comprising 0 to 2 weight percent menthol.

14. The method of any one of claims 8 to 13, wherein the first cooling agent is not encapsulated prior to mixing the first cooling agent with the gum base composition.

15. A chewing gum composition prepared according to the method of any one of claims 8 to 14.

Description:
CHEWING GUM COMPOSITIONS HAVING CONTROLLED RELEASE OF COOLING AGENTS AND METHODS OF MANUFACTURE

BACKGROUND

[0001] Chewing gum compositions can include a variety of different ingredients including various flavors or sweeteners. These flavors and sweeteners are generally provided in a water soluble portion of the chewing gum, and are released into the mouth of the chewer as the gum is chewed. In addition to flavors and sweeteners, numerous active agents can be added to provide the chewing gum with a desired sensation (e.g., cooling, warming, etc.). Many substances are known to provide a sensation of cooling on application and are termed "cooling agents." Exemplar}' cooling agents include menthol, isopulegol, 3-(l- menthoxy)propane- 1 ,2-diol, 3-(l-menthoxy)-2-methylpropane-l,2-diol, p-menthane-2,3-diol, p-menthane-3,8-diol, 6-isopropyl-9-methyl-i ,4-dioxaspiro[4,5] decane-2-methanoI, menthyl succinate and its alkaline earth metal salts, trimethyicyclohexanol, N-ethyl-2-isopropyl-5- methylcyclohexanecarboxamide, Japanese mint oil, peppermint oil, menthone, menthone glycerol ketai, menthyl lactate, 3-(l-menthoxy)ethan-l-ol, 3-(l-menthoxy)propan-l-ol, 3-( l- menthoxy)butan-l-ol, 1-menthyiacetic acid N-ethylamide, l-menthyl-4-hydroxypentanoate, 1- menthyl-3-hydi xybutyrate, N,2,3-trimethyl-2-(l-methylethyl)-butanamide, N-ethyl-t-2-c-6 nonadienamide, N,N -dimethyl menthyl succinamide, and menthyl pyrrolidone carboxylate.

[0002] One issue in the manufacture and formulation of chewing gum including a cooling agent is prolonging the release of the cooling agent during the chew. It is desirable to extend the perceived cooling sensation for the longest possible time. There have been efforts directed to enhancing the use of cooling agents within a chewing gum composition to control their release from the gum and to enhance the flavor. For example, the cooling agents can be treated to modify their release from the chewing gum. or can be used in a chewing gum coating.

[0003] Despite the existence of numerous cooling agents and the research efforts that have been conducted to date, there is a continuing need for a chewing gum composition that exhibits a long-lasting cooling sensation as the gum is chewed.

BRIEF SUMMARY

[0004] One embodiment is a chewing gum composition comprising a water insoluble gum base phase comprising a gum base composition and a first cooling agent comprising 0.01 to I weight percent N-ethyl-2,2-diisopropyIbutanamide; and a water soluble phase comprising a second cooling agent comprising 0.005 to 0.3 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate; and 0.005 to 0.3 weight percent N,2,3-trimethyl-2- isopropyl butanamide.

[0005] Another embodiment is a method of making a chewing gimi composition, the method comprising mixing a first cooling agent with a gum base composition to provide a gum base phase comprising 0.01 to 1 weight percent N-ethyI-2,2-diisopropyIbutanamide; and combining a w r ater soluble phase with the gum base phase to provide the chewing gum composition, wherein the water soluble phase comprises a second cooling agent comprising 0.005 to 0.3 weight percent ethyl 3-(p-menthane-3-carboxamido)acetate; and 0.005 to 0.3 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

[0006] Another embodiment is a chewing gum composition prepared according to the above-described method.

[0007] These and other embodiments are described in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The following Figures are exemplary embodiments:

[0009] FIG. 1 shows the cooling intensity over time for the gum composition according to Comparative Example 1.

[0010] FIG. 2 shows the cooling intensity over time for the gum composition according to Example I .

[001 1] FIG. 3 shows the cooling intensity over time for the gum composition according to Example 2.

[0012] FIG. 4 shows the cooling intensity over time for the gum composition according to Example 3.

DETAILED DESCRIPTION

[0013] The present inventors have determined that careful selection of particular cooling agents and their location within a chewing gum composition unexpectedly provides a prolonged cooling sensation, attributed to the extended release of the cooling agents from the gum composition. Specifically, the present inventors have determined that prolonged release profiles can be obtained due to the synergistic effect of including a cooling agent in the gum base phase of the composition and a second cooling agent in the w ater soluble phase of the composition, thus providing a long-lasting cooling effect.

[0014] Accordingly, one aspect of the present disclosure is a chewing gum composition. As used herein, the terms "gum," "chewing gum," and "bubble gum" are used interchangeably and are meant to include any gum composition. The chewing gum composition includes a water insoluble gum base phase comprising a gum base composition and a first cooling agent, and a water soluble phase comprising a second cooling agent. As used herein, the term "water-soluble" encompasses compounds which possess a water solubility of at least 1 gram per liter at 25 degree Celsius (°C). As used herein, the term "water-insoluble" encompasses compounds, which possess a water solubility of less than at least 1 gram per liter at 25°C.

[0015] Cooling agents, also known as coolants, are additives that provide a cooling or refreshing effect in the mouth, in the nasal cavity, or on skin. Menthyl-based coolants as used herein include menthol and menthol derivatives. Menthol (also known as 2-(2-propyl)- 5-methyl-l-cyclohexanol) is available in artificial form, or naturally from sources such as peppermint oil. Menthol derivatives include menthyl ester based and menthyl carboxamide- based cooling compounds such as menthyl carboxamide, monomenthyl succinate, dimenthyl succinate, monomenthyl methyl succinate, monomenthyl glutarate, dimenthyl glutarate, menthyl 2 pyrrolidone-5 carboxylate, monomenthyl 3-methyl maleate, menthyl acetate, menthyl lactate, dimenthyl lactate, menthyl salicylate, 2-isopropanyi-5-methylcyciohexanol, 3-L-menthoxypropane-l,2 diol, menthane, menthone, menthone ketals, menthone glycerol ketals, N-ethyl-p-menthane-3-carboxamide (WS-3), or a combination thereof. Additional menthyl-based coolants, specifically menthyl carboxamides, are described in U.S. Patent No. 7,923,577 to Bardsley et al. Other cooling agents include, for example, 2-mercapto-cyclo- decanone, hydroxycarboxylic acids with 2 to 6 carbon atoms, xylitol, er thritol, alpha- dimethyl succinate, acyclic carboxamides such as N,2,3-trimethyl-2-isopropyl butanamide (WS-23), N-ethyl-2,2-diisopropyibutanamide (ICE 10,000 or ICE- 1 OK), and combinations thereof. Additional cooling agents include the 1-tert-butyicyclohexanecarboxamides described in U.S. Patent Application Publication Nos. US 2011/0070171 Al and US

2011/0070329 Al of Kazimierski et al.

[0016] The chewing gum composition of the present disclosure includes a w r ater insoluble gum base phase comprising a first cooling agent comprising N-ethyl-2,2- diisopropylbutanamide (ICE 10,000 or ICE- 1 OK) in an amount of 0.01 to 1 weight percent, based on the total weight of the chewing gum composition. Within this range, the first cooling agent can be present in an amount of 0.1 to 0.5 weight percent, or 0.1 to 0.3 weight percent, or 0.15 to 0.25 weight percent, or 0.2 to 0.25 weight percent. In some embodiments, the first cooling agent is not encapsulated prior to mixing the first cooling agent with the gum base composition. [0017] In addition to the first cooling agent, the water insoluble gum base phase also includes a gum base composition. The gum base composition can vary depending upon various factors including the type of base desired, the consistency of gum desired, and the other components used in the composition to make the final chewing gum product. The gum base composition can include any water-insoluble gum base, and includes those gum bases utilized for chewing gums and bubble gums. Illustrative examples of suitable polymers in gum bases include both natural and synthetic elastomers and rubbers, for example, substances of vegetable origin such as chicle, crown gum. nispero, rosadinha, jelutong, perillo, niger gutta, tunu, balata, gutta-percha, lechi-capsi, sorva, gutta kay, and the like, and combinations thereof.

[0018] Synthetic elastomers include high- and low-molecular weight elastomers. Useful high molecular weight elastomers include butadiene-styrene copolymers,

pohisoprene, polyisobutylene, isobutylene-isoprene copolymers, polyethylene, combinations thereof, and the like. Useful low-molecular weight elastomers include polybutene, polybutadiene, polyisobutylene, and combinations thereof. Suitable gum bases can also include vinyl polymeric elastomers such as poly( vinyl acetate) (PVA), polyethylene, vinyl copolymeric elastomers such as copolymers of vinyl acetate and vinyl laurate, copolymers of vinyl acetate and vinyl stearate, copolymers of ethylene and vinyl acetate, poly(vinyl alcohol) and combinations thereof. When utilized, the number average molecular weight of the vinyl polymers can range be 3,000 to 94,000 Daltons (Da). Vinyl polymers such as polyvinyl alcohol) and poly( vinyl acetate) can have a number average molecular weight of 8,000 to 65,000 Da. Furthermore, any combination of the aforementioned high- and low-molecular weight, natural and synthetic elastomers, and rubbers can be used as a gum base.

[0019] The amount of gum base employed will vary greatly depending upon various factors such as the type of base used, the consistency of the gum desired, and the other components used in the composition to make the final chewing gum product. In general, the gum base will be present in an amount of 5 to 94 weight percent of the final chewing gum composition, hi some embodiments, the gum base amount is 15 to 45 weight percent, specifically 15 to 35 weight percent, more specifically 20 to 30 weight percent, based on the total weight of the chewing gum composition.

[0020] The gum base composition can contain conventional elastomer plasticizers to aid in softening the elastomer base component, for example terpene resins such as polymers derived from alpha-pinene, beta-pinene, or d-Iimonene; methyl, glycerol or pentaerythritol esters of rosins or modified rosins and gums, such as hydrogenated, dimerized or polymerized rosins, or combinations comprising at least one of the foregoing resins; the pentaerythritol ester of partially hydrogenated wood or gum rosin; the pentaerythritol ester of wood or gum rosin; the glycerol ester of wood rosin; the glycerol ester of partially dimerized wood or gum rosin; the glycerol ester of polymerized wood or gum rosin; the glycerol ester of tall oil rosin; the glyc erol ester of wood or gum rosin; the partially hydrogenated wood or gum rosin; the partially hydrogenated methyl ester of wood or rosin; and the like. Any combination of the foregoing elastomer plasticizers can be used to soften or adjust the tackiness of the elastomer base component. The elastomer plasticizer can be used in amounts of 5 to 75 weight percent of the gum base composition, specifically 45 to 70 weight percent of the gum base composition.

[0021] Suitable softeners include lanolin, palmitic acid, fatty acids such as palmitic acid and oleic acid and stearic acid, sodium stearate, potassium stearate, glyceryl triacetate, glyceryl lecithin, glyceryl monostearate, propylene glycol monostearate, mono-, di- and triglycerides, acetylated monoglyceride, glycerine, lecithin, diacetin, and combinations thereof. Other suitable softeners include waxes. Waxes, for example, natural and synthetic waxes, hydrogenated vegetable oils, petroleum waxes such as poiyurethane waxes, polyethylene waxes, paraffin waxes, microcrystalline waxes, fatty waxes, sorbitan monostearate, tallow, cocoa butter, and the like can also be incorporated into the gum base to obtain a variety of desirable textur es and consistency properties. In some embodiments, the softener is present in amounts of up to 30 weight percent of the gum base composition, specifically 3 to 20 weight percent of the gum base composition.

[0022] When a wax is present in the gum base composition, it softens the polymeric elastomer mixture and improves the elasticity of the gum base composition. The waxes employed can have a melting point below 60°C, and preferably 45 to 55°C. The low melting wax can be a paraffin wax. The wax can be present in the gum base in an amount of 6 to 10 weight percent, and preferably 7 to 9.5 weight percent, based on the total weight of the gum base composition.

[0023] In addition to the low r melting point waxes, waxes having a higher melting point can be used in the gum base in amounts up to 5 weight percent of the gum base. Such high melting waxes include beeswax, vegetable wax, rice bran wax, candelilla wax, carnuba wax, polyethylene wax, microcrystalline wax, most petroleum waxes, and the like, and mixtures thereof.

[0024] The gum base composition can include effective amounts of bulking agents such as mineral adjuvants, which can serve as fillers and textural agents. Suitable mineral adjuvants include calcium carbonate, magnesium carbonate, alumina, aluminum hydroxide, aluminum silicate, talc, tricalcium phosphate, tricalcium phosphate and the like, which can serve as fillers and textural agents. These fillers or adjuvants can be used in the gum base in various amounts. Specifically the amount of filler, when used, will be present in an amount of greater than 15 to 40 weight percent, specifically 20 to 30 weight percent, based on the weight of the gum base composition.

[0025] In addition to the water insoluble gum base phase, the chewing gum composition comprises a water soluble phase. The water soluble phase includes a second cooling agent comprising ethyl 3-(p-menthane-3-carboxamido)acetate in an amount of 0.005 to 0.3 weight percent, and N,2,3-trirneihyl-2-isoprop i butanamide in an amount of 0.005 to 0.3 weight percent, wherein weight percent of each is based on the total weight of the chewing gum composition. Within the above range, the ethyl 3-(p-menthane-3- carboxamido)acetate can be present in an amount of 0.01 to 0.1 weight percent, or 0.1 to 0.05 weight percent, or 0.02 to 0.04 weight percent, or 0.025 to 0.025 weight percent. Also within the above range, the N,2,3-trimethyl-2-isopropyl butanamide can be present in an amount of 0.0075 to 0.15, or 0.0075 to 0.02, or 0.0075 to 0.01 or 0.0075 to 0.0125. In some embodiments, the second cooling agent is not encapsulated prior to preparation of the water soluble phase.

[0026] In some embodiments, the water soluble phase further includes one or more flavoring agents (also known as flavorants, flavorings, or flavors}. Suitable flavoring agents can include artificial and natural flavors that are generally known, for example synthetic flavor oils, natural flavoring aromatics or oils, oleoresins, extracts derived from plants, leaves, flowers, fruits, and the like, and combinations comprising at least one of the foregoing flavorants. Examples of artificial, natural and synthetic fruit flavorings include coconut, coffee, chocolate, vanilla, lemon, grapefruit, orange, lime, yazu, sudachi, menthol, licorice, caramel, honey, peanut, walnut, cashew, hazelnut, almonds, pineapple, strawberry, raspberry, blackberry, tropical fruits, cherries, cinnamon, peppermint, wintergreen, spearmint, eucalyptus, and mint, fruit essence such as from apple, pear, peach, grape, blueberry, strawberry, raspberry, cherry, plum, pineapple, apricot, banana, melon, apricot, ume, cherry, raspberry, blackberry, tropical fruit, mango, mangosteen, pomegranate, papaya, and the like, and combinations thereof.

[0027] in some embodiments, the water soluble phase comprises a fruit flavor, a mint flavor, or a combination thereof. In some embodiments, the water soluble phase preferably comprises a fruit flavor, for example a fruit flavor comprising watermelon flavor, strawberry flavor, banana flavor, mango flavor, blueberry flavor, or a combination thereof. In an embodiment, the fruit flavor comprises watermelon flavor. In some embodiments, the water soluble phase can include a mint flavor, for example menthol. In some embodiments, the chewing gum composition further comprises 0 to 2 weight percent of menthol, based on the total weight of the chewing gum. in some embodiments, the chewing gum composition excludes menthol. In some embodiments, the chewing gum composition comprises greater than 0 to 2 weight percent menthol.

[0028] The flavoring agents can be used in many distinct physical forms, including liquid and dried forms. The flavoring agents can be used in the amount of 0.01 to 30 weight percent of the gum composition depending on the desired intensity. Preferably, the content of the flavoring agents is in the range of 0.2 to 3 weight percent of the chewing gum

composition

[0029] The water soluble phase can further include various additives including bulk sweeteners, high intensity sweeteners, flavor modulators or potentiators, coloring agents, medicaments, oral care agents, throat care agents, breath fresheners, mineral adjuvants, bulking agents, acidulants, buffering agents, sensates (e.g., warming agents, tingling agents, effervescing agents), thickeners, mouth moisteners, flavor enhancing compositions, antioxidants (e.g., butylated hydroxytoluene (BHT), butylated hydroxyanisole (BRA), or propyl gallate), preservatives, emulsifiers, thickening agents, and the like. Some of these additives can serve more than one purpose. For example, a sweetener such as sucrose, sorbitol or other sugar alcohol, or combinations thereof, can also function as a bulking agent. In addition, combinations comprising the foregoing additives are often used.

[0030] In some embodiments, the chewing gum includes a sweetening agent to provide a sweet taste to the gum composition. Sweetening agents can include sugar sweeteners, sugarless sweeteners, high intensity sweeteners, or a combination of at least two of the foregoing sweetening agents.

[0031] Sugar sweeteners generally include saccharides. Suitable sugar sweeteners include monosaccharides, disaccharides, and polysaccharides such as sucrose (sugar), dextrose, maltose, dextrin, xylose, ribose, glucose, mannose, galactose, fructose (levulose), lactose, invert sugar, fructooligosaccharide syrups, partially hydrolyzed starch, corn syrup solids, such as high fructose corn syrup, and mixtures thereof.

[0032] Suitable sugarless sweetening agents include sugar alcohols (or polyols) such as sorbitol, xylitol, mannitol, galactitol, maititol, hydrogenated isomaltulose (isomalt), lactitol, erythritol, hydrogenated starch hydrolysate, stevia and mixtures thereof. Suitable hydrogenated starch hydrolysates include those disclosed in U.S. Pat. No. 4,279.931 to Verwaerde et al. and various hydrogenated glucose syrups and'Or powders, which contain sorbitol, hydrogenated disaccharides, hydrogenated higher polysaccharides, or mixtures thereof. Hydrogenated starch hydrolysates are primarily prepared by the controlled catalytic hydrogenation of corn syrups. The resulting hydrogenated starch hydrolysates are mixtures of monomeric, dimeric, and polymeric saccharides. The ratios of these different saccharides give different hydrogenated starch hydrolysates different properties. Also useful are mixtures of hydrogenated starch hydrolysates. such as those sold under the trade name LYCASIN by Roquette Freres of France, and those sold under the trade name HYSTAR by Lonza, Inc., of Fair Lawn, New Jersey, USA.

[0033] A "high intensity sweetener" as used herein means agents having a sweetness at least 100 times that of sugar (sucrose) on a per weight basis, specifically at least 500 times that of sugar on a per weight basis. In one embodiment the high intensity sweetener is at least 1 ,000 times that of sugar on a per weight basis, more specifically at least 5,000 times that of sugar on a per weight basis. The high intensity sweetener can be selected from a wide range of materials, including water-soluble sweeteners, water-soluble artificial sweeteners, water-soluble sweeteners derived from naturally occurring water-soluble sweeteners, dipeptide based sweeteners, and protein based sweeteners. Any combination comprising two or more high intensity sweetener can be used. One or more of the high intensity sweeteners can further be combined with one or more of the foregoing sweeteners or sweetening agents. The high intensity sweetener can be used in a variety of distinct physical forms, for example those known in the art to provide an initial burst of sweetness and/or a prolonged sensation of sweetness. Without being limited thereto, such physical forms include free forms (e.g., spray dried or powdered), beaded forms, encapsulated forms, and combinations of the foregoing forms.

[0034] Without being limited to particular sweetening agents, representative categories and examples include: (1) water-soluble sweetening agents such as

dihydrochaicones, monellin, steviosides, Rebaudioside A, Rebaudioside B, Rebaudioside C, glycyrrhizin, dihydroflavenol, and sugar alcohols such as sorbitol, mannitol, maltitoi, monatin, and L-aminodicarboxyiic acid aminoaikenoic acid ester amides, such as those disclosed in U.S. Pat. No. 4,619,834 to Zanno et al., and combinations thereof; (2) water- soluble artificial sweeteners such as saccharin, soluble saccharin salts, i.e., sodium or calcium saccharin salts, cyclamate salts, acesulfame salts, such as the sodium, ammonium or calcium salt of 3,4-dihydro-6-methyl-l,2,3-oxathiazine-4-one-2,2-dioxide, the potassium salt of 3.4-dihydi -6-methyl-l,2,3-oxathiazine-4-one-2,2-dioxide (Acesulfame-K), the free acid form of saccharin, and combinations thereof; (3) dipeptide based sweeteners, for example the L-aspartic acid derived sweeteners such as L-aspartyl-L-phenylaianine methyl ester

(Aspartame) and materials described in U.S. Pat. No. 3,492,131 to Schlatter, L-alpha- aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alaninamide hydrate (Alitame), methyl esters of L-aspartyl-L-phenyiglycine and L-aspartyl-L-2,5-dihydrophenylglycine, L-alpha-aspartyl- L-phenylglycine methyl ester, L-aipha-aspartyl-L-2,5-dihydrophenylglycine methyl ester, L- aspartyl-2,5-dihydro-L-phenylalanine; L-alpha-aspartyl-2,5-dihydrophenylalanine methyl ester, L-aspartyl-L-(l-cyclohexen)-alanine, N-(N-(3,3-dimethylbutyl)-L-alpha-aspartyl)-L- phenylalanine methyl ester (Neotame), or a combination thereof; (4) derivatives of water- soluble sweeteners, such as steviosides, Rebaudioside A, Rebaudioside B, Rebaudioside C, chlorinated derivatives of ordinary sugar (sucrose), e.g., chlorodeoxysugar derivatives such as derivatives of chlorodeoxysucrose or chlorodeoxygaiactosucrose, known, for example, under the product designation of Sucraiose; examples of chlorodeoxysucrose and

chlorodeoxygaiactosucrose derivatives include l-chloro-l'-deoxysucrose; 4-chloro-4-deoxy- alpha-D-galactopyranosyl-alpha-D-fhictofuraiioside, or 4-cmoro-4-deoxygalactosucrose; 4- chloro-4-deoxy-alpha-D-galactopyranosyl- 1 -chloro-l-deoxy-beta-D-fructofuranoside, 4, 1 '- dichloro-4, 1 '-dideoxygalactosucrose; ,6'-dichloro-l',6'-dideoxysucrose; l,6-dichloro-l,6- dideoxy-P-D-fiuctofmanosyl-4-chloro-4-deoxy-a-D-galactop Tanoside; 4-chloro-4-deoxy- alpha-D-gaiactopyranosyl- 1 ,6-dichloro-l,6-dideoxy-beta-D-fructofuranoside, or 4, 1 ',6'- trichloiO-4,r,6'-trideoxygalactosuci se; 4,6-dichloro-4,6-dideoxy-alpha-D-galactopyranosyl- 6-chloro-6-deoxy-beta-D-fmctofuranoside, or 4,6,6'-trichloi -4,6,6'-trideoxygalactosucrose; 6,1 ',6'-trichloro-6, 1 ',6'-trideoxysucrose; 4,6-dichloro-4,6-dideoxy-aipha-D-galacto-pyranosyl- 1 ,6-dichloro-l,6-dideox y-beta-D-fructofuranoside, or 4,6,r,6'-tetrachloro4,6,r,6'- tetradeoxygalacto-sucrose; 4,6,l',6'-tetradeoxy-sucrose, and combinations thereof; (5) protein based sweeteners such as thaumatococcous danielli, thaumatin, talin; mogrosides (lo han guo); and combinations thereof; and (6) amino acid based sweeteners.

[0035] In some embodiments, the sweeteners include sorbitol, mannitol, aspartame, acesulfame potassium salt, and combinations thereof. The sweeteners can be present in a suitable amount depending upon the desired level of sweetness. In some embodiments the sweeteners are present in an amount of 35 to 80 weight percent, or 45 to 75 weight percent, or 50 to 65 weight percent of the chewing gum composition.

[0036] Additional bulking agents (carriers, extenders) suitable for use include sweetening agents such as monosaccharides, disaccharides, polysaccharides, sugar alcohols, polydextrose, maltodextrins, minerals, such as calcium carbonate, talc, titanium dioxide, dicalcium phosphate, and combinations thereof. Bulking agents can be used in amounts up to 90 weight percent of the chewing gum composition, specifically 40 to 70 weight percent, or 50 to 65 weight percent of the chewing gum composition.

[0037] Suitable emulsifiers include distilled monoglycerides, acetic acid esters of mono and diglycerides, citric acid esters of mono and diglycerides, lactic acid esters of mono and diglycerides, mono and diglycerides, polyglycerol esters of fatty acids, ceteareth-20, polyglycerol polyricinoleate, propylene glycol esters of fatty acids, polyglyceryl laurate, glyceryl cocoate, gum arable, acacia gum, sorbitan monostearates, sorbitan tristearates, sorbitan monolaurate, sorbitan monooleate, sodium stearoyl lactylates, calcium stearoyl lactylates, diacetyl tartaric acid esters of mono- and diglycerides, glyceryl tricaprylate-caprate / medium chain triglycerides, glyceryl dioleate, glyceryl oleate, glyceryl iacto esters of fatty acids, glyceryl lacto palmitate, glyceryl stearate, glyceryl laurate, glycerly dilaurate, glyceryl monorieinoleate, triglyceryl monostearate, hexaglyceryl distearate, decaglyceryi

monostearate, decaglyceryi dipalmitate, decaglyceryi monooleate, polyglyceryl 10 hexaoleate, medium chain triglycerides, caprylic/capric triglyceride, propylene glycol monostearate, poiysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, polysorbate 65, hexyiglyceryl distearate, triglyceryl monostearate, the poly(oxyethyiene) sorbitan fatty acid esters sold under the trade name TWEEN, the sorbitan fatty acid esters sold under the trade name SPAN, stearoyl lactylates, calcium stearoyl-2-iactylate, sodium stearoyl-2- lactylate lecithin, ammonium phosphatide, sucrose esters of fatty acids, sucroglycerides, propane- 1,2-diol esters of fatty acids, and combinations thereof.

[0038] Suitable thickening agents include cellulose ethers including

hydroxyethyiceiiulose, hydroxypropylmethylcellulose, and hydroxypropylcellulose, methylceliulose, carboxymethylcellulose, and combinations thereof. Additional polymers useful as thickeners include the acrylic acid polymers and copolymer sold under the trade name CARBOMER, poly(vinyi pyrrolidone), poly( vinyl alcohol), sodium alginate, polyethylene glycol, natural gums like xanthan gum, tragacantha, guar gum, acacia gum, arable gum; water-dispersibie polyacrylates like poly(acrylic acid), methyl methacrylate copolymers, carboxy vin l copolymers, and combinations thereof.

[0039] Coloring agents (colorants, colorings) can be used in amounts effective to produce a desired color for the chewing gum composition. Suitable coloring agents include pigments, which can be incorporated in amounts up to 6 weight percent of the chewing gum composition. For example, titanium dioxide can be incorporated in amounts up to 2 weight percent, and specifically less than 1 weight percent by weight of the chewing gum composition. Suitable coloring agents also include natural food colors and dyes suitable for food, drug, and cosmetic applications.

[0040] Suitable colors include annatto extract (El 60b), bixin, norbixin, astaxanthin, dehydrated beets (beet powder), beetroot red/betanin (El 62), ultramarine blue, canthaxanthin (E161g), cryptoxanthin (E161c), rubixanthin (E161d), violanxanthin (E161e), rhodoxanthin (E161f), caramel (E150(a-d)), p-apo-8'-carotenal (E160e), β-carotene (E l 60a), alpha carotene, gamma carotene, ethyl ester of beta-apo-8 carotenal (El 601), flavoxanthin (E161a), lutein (El 61b), cochineal extract (E120), carmine (El 32), carmoisine/azorubine (E122), sodium copper chlorophyllin (E 141 ), chlorophyll (El 40), toasted partially defatted cooked cottonseed flour, ferrous gluconate, ferrous lactate, grape color extract, grape skin extract (enocianina), anthocyanins (El 63), haematococcus algae meal, synthetic iron oxide, iron oxides and hydroxides (El 72), fruit juice, vegetable juice, dried algae meal, tagetes (Aztec marigold) meal and extract, carrot oil, com endosperm oil, paprika, paprika oleoresin, phaffia yeast, riboflavin (El 01 ), saffron, titanium dioxide, turmeric (El 00), turmeric oleoresin, amaranth (E123), capsanthin/capsorbin (E160c), lycopene (E160d), FD&C blue #1 , FD&C blue #2, FD&C green #3, FD&C red #3, FD&C red #40, FD&C yellow #5 and FD&C yellow #6, tartrazine (El 02), quinoline yellow (El 04), sunset yellow (El 10), ponceau (E124), erythrosine (E127), patent blue V (E131), titanium dioxide (E171 ), aluminum (E173), silver (E174), gold (E175), pigment aibine/lithol rubine BK (El 80), calcium carbonate (El 70), carbon black (E153), black P /brilliant black B (E151), green S/acid brilliant green BS (El 42), FD&C aluminum lakes, and combinations thereof.

[0041] Various food-grade acids can be included in the chewing gum composition, and include, for example, acetic acid, citric acid, fumaric acid, hydrochloric acid, lactic acid and nitric acid as well as sodium citrate, sodium bicarbonate, sodium carbonate, sodium or potassium phosphate, magnesium oxide, potassium metaphosphate, sodium acetate, and combinations thereof. The acidulants can be present in a suitable amount depending upon the desired level of intensity. In some embodiments, the acidulants are present in an amount of 0.1 to 3 weight percent of the chewing gum composition. Within the range of 0.1 to 3 weight percent, the acidulants can be present in an amount of 0.5 to 2.5 weight percent, based on the total weight of the chewing gum composition.

[0042] In some embodiments, the chewing gum can further include unencapsulated food-grade acids. Suitable unencapsulated acids include, for example, adipic acid, ascorbic acid, aspartic acid, benzoic acid, citric acid, fumaric acid, glutamic acid, maleic acid, malic acid, oxalic acid, phosphoric acid, sorbic acid, succinic acid, tartaric acid, and mixtures thereof. In some embodiments, the unencapsulated acids include citric acid, malic acid, and mixtures thereof. In some embodiments, the unencapsulated food-grade acids are present in an amount 0.1 to 2.0 weight percent, or 0.25 to 1.5 weight percent, or 0.5 to 1.0 weight percent of the chewing gum composition.

[0043] In an embodiment, the chewing gum compos ion comprises a water insoluble gum base phase comprising a gum base composition and a first cooling agent comprising 0.1 to 0.3 weight percent N-ethyl-2,2-diisopropylbutanamide and a water soluble phase comprising a second cooling agent comprising 0.01 to 0.05 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate and 0.005 to 0.02 weight percent N,2,3-trimethyi-2- isopropyl butanamide.

[0044] In an embodiment, the chewing gum composition comprises a water insoluble gum base phase comprising a gum base composition and a first cooling agent comprising 0.15 to 0.25 weight percent N-ethyl-2,2-diisopropylbutanamide and a water soluble phase comprising a second cooling agent comprising 0.025 to 0.035 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate and 0.0075 to 0.0125 weight percent N,2,3-trimethyl-2- isopropyi butanamide.

[0045] in an embodiment, the chewing gum composition comprises a water insoluble gum base phase comprising a gum base composition and a first cooling agent comprising 0.2 to 0.25 weight percent N-ethyl-2,2-diisopropylbutanamide and a water soluble phase comprising a second cooling agent comprising 0.025 to 0.035 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate and 0.0075 to 0.0125 weight percent ,2,3-trimethyi-2- isopropyl butanami de.

[0046] The gum compositions disclosed herein can be coated or uncoated, and be in the form of slabs, sticks, pellets, balls, and the like. The composition of the different forms of the gum compositions will be similar but can vary with regard to the ratio of the ingredients. For example, coated gum compositions can contain a lower percentage of softeners. Pellets and balls can have a chewing gum core, which has been coated with either a sugar solution or a sugarless solution to create the hard shell. Slabs and sticks are usually formulated to be softer in texture than the chewing gum core. In some cases, a hydroxy fatty acid salt or other surfactants can have a softening effect on the gum base. In order to adjust for any potential undesirable softening effect that the surfactants can have on the gum base, it can be beneficial to formulate a slab or stick gum having a firmer texture than usual (i.e., use less conventional softener than is typically employed). [0047] Another aspect of the present disclosure is a method of making a chewing gum having improved cooling. These chewing gum compositions can be prepared using any standard techniques and equipment known to those skilled in the art. The method comprises mixing a first cooling agent with a gum base composition to provide a gum base phase comprising 0.01 to 0.1 weight percent N-ethyl-2,2-diisopropylbutanamide. In some embodiments, the first cooling agent is mixed with substantially all of the gum base composition. Stated another way, the first cooling agent is mixed with at least 95%, or at least 99%. or 100% of the gum base composition. The method further comprises combining a water soluble phase with the gum base phase to provide the chewing gum composition. The resulting chewing gum composition includes 0.005 to 0.3 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate and 0.005 to 0.3 weight percent N,2,3-trimethyI-2- isop opyl butanamide present in the water soluble phase, wherein weight percent is based on the total weight of the chewing gum composition.

[0048] In an embodiment, the gum base can be heated to a temperature sufficiently high to soften the base without adversely affecting the physical and chemical make-up of the base, which can vary depending on the composition of the gum base used, and can be readily determined by those skilled in the art without undue experimentation. For example, the gum base can be melted at 60 to 160°C, or 60 to 100°C, or 70 to 90°C, for a period of time sufficient to render the base molten, just prior to being admixed with the first cooling agent. The remaining ingredients (e.g., plasticizers, fillers, bulking agents, sweeteners, softening agents, and coloring agents) can be added incrementally following thorough mixing of the gum base composition with the first cooling agent.

[0049] In some embodiments, flavoring agents, if any, and the second cooling agent can be premixed, prior to addition to the gum base phase. Following addition of the second cooling agent to the gum base phase, mixing is continued until a uniform mixture of the gum composition is obtained. Thereafter the gum composition mixture can be formed into desirable gum shapes, for example, stick, slab, pellet, ball, and the like. The sized chewing gum can be conditioned for about one day prior to packaging the chewing gum. An exemplary method of making the chewing gum composition is further described in the working exam les below.

[0050] The chewing gum compositions and methods of making described herein are further illustrated by the following non-limiting examples.

EXAMPLES [0051] The cooling agents used to prepare the chewing gum compositions of the following Examples are provided in Table 1.

Table 1

[0052] Chewing gum compositions were prepared according to the following procedure and using the components and amounts described in Tables 2-4. The amount of each component is provided in weight percent, based on the total weight of the chewing gum composition.

[0053] The chewing gum compositions were prepared by first mixing the gum base, lecithin, and acetyiated monoglycerides at a temperature of 85°C. The temperature of the gum base mixture was adjusted to 80°C, and, for Examples 1-3, N-ethyi-2,2- diisopropylbutanamide (Ice- 1 OK) cooling agent was added to form a gum base composition in the amounts shown in Table 2. The gum base composition including the cooling agent was mixed at a temperature of 80°C for 1 minute. The blended gum base composition was further mixed with sorbitol (obtained as NEOSORB P60A from Roquette), crystalline xylitol, FD&C RED 40 as a colorant, and glycerin in the amounts shown in Table 2. The gum base phase was mixed for 3.5 minutes.

Table 2

[0054] Separately, a first part of the water soluble phase of the chewing composition including a flavor blend was prepared using watermelon flavor (obtained as FIR 541131 6T from Firmenich), WS-23, WS-5 (only for Examples 1-3), and medium chain triglyceride (MCT) oil in the amounts shown in Table 3. The first part of the water soluble phase (e.g., the premixed flavor blend) was then combined with the above-described gum base phase while mixing.

Table 3

[0055] In a final stage of mixing, a second part of the water soluble phase of the chewing gum composition including the acids, additional solid watermelon flavor (obtained as FLEXAROME 880473 FBS1504 from Firmenich), and sweeteners were added to the above mixture comprising the gum base phase and the first part of the water soluble phase in the amounts shown in Table 4.

Table 4

Intensive sweetener comprises aspartame (71.3 wt.% based on the weight of the intensive sweetener) and acesulfame potassium (28.7 wt.% based on the weight of the intensive sweetener)

[0056] After all of the above-described mixing stages were completed, the chewing gum compositions of Comparative Example 1 and Examples 1-3 were cooled. The chewing gum compositions were dusted with mannitol as needed to provide a coating. The chewing gum was formed by rolling and scoring into chewing gum pieces.

[0057] Each of the chewing gum compositions of Comparative Example 1 and Examples 1-3 were chewed by a panel of human subjects to assess the cooling sensation using a quantitative descriptive analysis (QDA). Samples of each chewing gum composition were chewed by 12 people with 3 or 4 replications of each example. Each panelist rated the cooling intensity of the chewing gum by graphically indicating a rating on a line intensity scale. The results were collected and electronically quantified using sensory evaluation software to fit a 100-point scale. The duration of the cooling intensity of each composition was determined by comparing the cooling intensity ratings over time. The chewing gum compositions of Examples 1-3 were shown to provide improved cooling intensity, especially at 10 and 20 minute chew times, compared to Comparative Example 1.

[0058] The cooling intensity of Comparative Example 1 and Examples 1-3 is summarized in Table 3, and shown in Figures 1-4. Each of the chewing gum compositions of Examples 1-3 showed an overall increase in the duration of perceived cooling sensation compared to a composition which did not include a cooling agent in the gum base phase of the composition (Comparative Example 1).

Table 3

[0059] Each of the compositions of Examples 1-3 achieved similar initial cooling intensity ratings of 34.3, 33.4, and 32.9 (based on a 100 point scale), respectively. These cooling intensities were also similar to the initial cooling intensity of 33 for the composition according to Comparative Example 1. The cooling intensity of Comparative Example 1 peaks around 1 minute of chewing with an intensity of 37.3, followed by a decrease to 29 at 20 minutes. In contrast, the chewing gum compositions of Examples 1-3 each exhibit a prolonged sensation, evidenced by the more gradual decline relative to Comparative Example 1. Both of Example 1 and 3 reach a peak cooling intensity of 35.3 and 37.5, respectively, after 5 minutes of chewing. Following 20 minutes of chewing, each of Examples 1-3 were perceived to have a high cooling intensity than the composition of Comparative Example 1.

[0060] Accordingly, the above examples demonstrate that the duration of cooling intensity of a chewmg gum composition can unexpectedly be extended by careful selection of cooling agents and their location within the chewing gum composition.

[0061] The chewing gum composition and method of making includes at least the following embodiments.

[0062] Embodiment 1 : A chewing gum composition comprising, a water insoluble gum base phase comprising a gum base composition and a first cooling agent comprising 0.01 to 1 weight percent N-ethyl-2,2-diisopropylbutanamide; and a water soluble phase comprising a second cooling agent comprising, 0.005 to 0.3 weight percent ethyl 3-(p- menthane-3-carboxamido)acetate; and 0.005 to 0.3 weight percent N,2,3-trimethyi-2- isopropyl butanamide.

[0063] Embodiment 2: The chewing gum composition of embodiment 1, wherein the first cooling agent comprises 0.1 to 0.5 weight percent N-ethyl-2,2-diisopropylbutanamide; and the second cooling agent comprises 0.01 to 0.1 weight percent ethyl 3-(p-menthane-3- carboxamido)acetate and 0.0075 to 0.15 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

[0064] Embodiment 3 : The chewing gum composition of embodiment 1 or 2, wherein the first cooling agent comprises 0.20 to 0.25 weight percent of N-ethyl-2,2- diisopropylbutanamide; and the second cooling agent comprises 0.025 to 0.035 weight percent ethyl 3-(p-menthane-3-carboxamido)acetate and 0.0075 to 0.0125 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

[0065] Embodiment 4: The chewing gum composition of any one of embodiments 1 to 3, wherein the water soluble phase further comprises a fruit flavor, a mint flavor, or a combination thereof.

[0066] Embodiment 5: The chewing gum composition of any one of embodiments 1 to 4, wherein the water soluble phase further comprises a fruit flavor comprising watermelon flavor, strawberry flavor, banana flavor, mango flavor, blueberry flavor, or a combination thereof.

[0067] Embodiment 6: The chewing gum composition of any one of embodiments 1 to 5, further comprising 0 to 2 weight percent menthol.

[0068] Embodiment 7: The chewing gum composition of any one of embodiments 1 to 6, wherein the first cooling agent and the second cooling agent are not encapsulated.

[0069] Embodiment 8: A method of making a chewing gum composition having improved cooling, the method comprising, mixing a first cooling agent with a gum base composition to provide a gum base phase comprising 0.01 to 1 weight percent N-ethyl-2,2- diisopropylbutanamide; and combining a water soluble phase with the gum base phase to provide the chewing gum composition, wherein the water soluble phase comprises a second cooling agent comprising, 0.005 to 0.3 weight percent ethyl 3-(p-menthane-3- carboxamido)acetate; and 0.005 to 0.3 weight percent N,2,3-trimethyi-2-isopropyi butanamide.

[0070] Embodiment 9: The method of embodiment 8, wherein the first cooling agent comprises 0.1 to 0.5 weight percent N-ethyl-2,2-diisopropylbutanamide; and the second cooling agent comprises 0.01 to 0.1 weight percent ethyl 3-(p-menfhane-3- carboxamido)acetate and 0.0075 to 0.15 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

[0071] Embodiment 10: The method of embodiment 8 or 9, wherein the first cooling agent comprises 0.20 to 0.25 weight percent of N-ethyi-2,2-c isopropyibutanamide; and the second cooling agent comprises 0.025 to 0.035 weight percent ethyl 3-(p-menthane-3- carboxamido)acetate and 0.0075 to 0.0125 weight percent N,2,3-trimethyl-2-isopropyl butanamide.

[0072] Embodiment 11: The method of any one of embodiments 8 to 10, wherein the water soluble phase further comprises a fruit flavor, a mint flavor, or a combination thereof.

[0073] Embodiment 12: The method of any one of embodiments 8 to 11, wherein the water soluble phase further comprises a watermelon flavor, strawberry flavor, banana flavor, mango flavor, blueberry flavor, or a combination thereof.

[0074] Embodiment 13: The method of any one of embodiments 8 to 12, further comprising 0 to 2 weight percent menthol.

[0075] Embodiment 14: The method of any one of embodiments 8 to 13, wherein the first cooling agent is not encapsulated prior to mixing the first cooling agent with the gum base composition.

[0076] Embodiment 15: A chewing gum composition prepared according to the method of any one of embodiments 8 to 14.

[0077] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

[0078] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0079] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or sub-range lying within the disclosed range. The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Further, it should further be noted that the terms "first," "second," and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. "Or" means "and/or". The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity).

Reference throughout the specification to "another embodiment," "an embodiment," and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.