METHODS AND COMPOSITIONS FOR PROTECTING
BEVERAGES FROM HEAT AND LIGHT STRESS
CROSS-REFERENCE OF RELATED APPLICATION
[01] This application claims priority of U.S. application serial No. 13/216,324, filed
August 24, 2012, hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[02] This invention relates to beverages and other beverage products that include juices
and/or colors derived from natural sources, such as finished beverages, concentrates,
syrups and the like. In particular, this invention relates to beverage products having
formulations for preventing or reducing color change.
BACKGROUND
[03] It has long been known to produce beverages of various formulations. Problems with
beverage formulations remain, however. Following manufacture, beverage products
are generally not refrigerated during distribution and may be subjected excessive heat
during transport and also during storage prior to sale. These environmental exposures
can affect beverage color. Similarly, exposure to light may have a bleaching effect
leading to color fading.
[04] In addition to fading, beverages can develop visual brown color, a phenomenon
known as "browning," which is a ubiquitous problem in the food and beverage
industry. Two types of browning occur: enzymatic browning and non-enzymatic
browning. Both can be promoted by various factors, including time, elevated storage
temperature, and air permeability of packaging material (carton, drum or glass).
[05] Inhibition and control of non-enzymatic browning depends on product composition,
storage, time, and temperature (Lozano 2006; Roig et al, 1999). Non-enzymatic
browning is driven by the Maillard reaction. The Maillard reaction produces
desirable brown colors in baked goods, frying or roasting. However, in beverage
applications, brown color is undesirable. In addition to color change, nutritional loss
occurs when essential amino acids and/or vitamin C is degraded.
[06] The Maillard reaction is a complex series of chemical interactions initiated by a
reaction between an amino acid and a reducing sugar, usually requiring the addition of
heat, which results in the formation of brown polymeric melanoidins (Ziderman et al,
1989). The sugar reacts with amino acids, producing a variety of odors, flavors, and
finally brown color. (Ibarz et al, 2008).
[07] Many chemicals contribute to browning colors and flavors. For example, furfural and
hydroxymethylfurfural (HMF) are characteristic compounds of the Maillard reaction.
Non-enzymatic browning also plays a role in acid-catalyzed thermal decomposition of
reducing sugars into reactive intermediates (Lee and Nagy, 1988). Formation of
HMF, 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF), and furfural result from
degradation of sugars and by degradation of ascorbic acid (Lee and Nagy 1996).
Melanins and other chemicals also contribute to the brown color.
[08] Because HMF is a recognized indicator of non-enzymatic browning, it is often used as
an index of deteriorative changes that take place during excessive heating. The HMF
content provides a measure of the degree of heating of the treated products during
processing and is thus considered a quality parameter for concentrated food products.
[09] In fruit juice concentrates, high temperature manufacturing processes, such as juice
concentration, fruit dehydration, or storage at improper temperature, are thought to
promote HMF formation. According to Garza et al. (1999) a significant increase in
HMF content during thermal treatment of peach puree occurred at several high
temperatures including 85, 90, and 98° C.
[10] Oxygen and heat are believed to be the principle drivers of ascorbic acid degradation
during juice processing, packaging, and storage. Oxidation reactions are accelerated at
higher temperatures thereby resulting in product degradation (Clegg 1964). From a
chemical degradation perspective, ascorbic acid is converted to dehydroascorbic acid
(DHAA) in a reversible aerobic pathway (Sawarnura, 2000). DHAA has the same
activity as Vitamin C. The subsequent irreversible conversion of DHAA to 2,3-
diketogulonic acid (DKGA) by oxidation causes a loss in Vitamin C activity. DKGA
can be further converted to furfural in aerobic and anaerobic pathways. The formation
of furfural through an aerobic pathway predominates over the anaerobic degradation
of ascorbic acid, being at one-tenth or up to one-thousandth of the rate of ascorbic
acid loss under aerobic conditions (Kefford, et. al. 1958). Furfural formation is
dependent on temperature, time, pH, concentration of juice and ascorbic acid content
(Kus, et. al. 2005).
[11] Various approaches to reducing browning have been explored. Chemicals such as
chelating agents, complexing agents, and enzyme inhibitors have been found to
reduce both enzymatic and non-enzymatic browning in fruits and fruit juices.
Chemical anti-browning agents have been commonly used to prevent browning of
fruits and fruit products. Anti-browning agents are compounds that act primarily on
the enzyme, react with the substrates and/or products of enzymatic catalysis, or
inactivate precursors of non-enzymatic pathways in a manner that inhibits colored
product formation.
[12] Adding SO2, Sn + (tin) or cysteine to concentrated lemon juice affects color during
storage. Beverages containing 125 ppm SO2 showed inhibited browning when stored
at 45° C. At higher levels (250 ppm), the degradation of ascorbic acid and the
formation of furfural and HMF were inhibited. In addition adding Sn + (1000 mg / kg
juice) reduced browning to about one-third the rate obtained in the absence of tin.
Other methods of inhibiting non-enzymatic browning include adding L-cysteine and
N-acetyl-L-cysteine (Nairn and others 1993). However, juices with added N-acetyl-Lcysteine
suffer from inferior aroma.
[13] Sulfites reduce o-quinone produced by PPO catalysis to the less reactive diphenol,
preventing development of brown melanins (Lozano 2006). Sulfite use is less
desirable, however, due to its tendency to induce severe allergic reactions in
susceptible individuals (Sapers 1993), and the FDA restricts sulfite use in certain fruit
and vegetable products for that reason. When added, sulfites may be used as sulfur
dioxide, sulfurous acid, sodium or potassium sulfite, bisulfite, or metabisulfite in nonenzymatic
browning applications as well. Maximum levels of 300, 500 and 2000 ppm
have been proposed for fruit juices, dehydrated potatoes, and dried fruit, respectively
(Taylor et. al. 1986).
Consumers have a wide range of choices ranging from 100% juices to juice drinks
containing lesser amounts of juice. Beverage producers need to provide quality
products in attractive packaging in order to insure a successful product in the
marketplace (Ucherek 2000). Thus, it is extremely important that manufacturers
manage the quality of product they are putting on the shelves to maintain customer
retention. Thermo-processing, packaging, storage, presence of components can all be
key drivers of product desirability. Loss of quality is exhibited by flavor/aroma
degradation, loss of vitamins and color, microbial growth, and browning. Quality loss
in juices can often be due to browning, accompanied by development of off-flavors
(Culver 2008) as well as the undesirable color. Any of these contributing factors of
quality loss can reduce consumer acceptance (Koca et al, 2003).
[15] Accordingly, it is an object of the invention to provide beverages and other beverage
products having desirable appearance, taste and health properties by reducing
undesirable color change. It is an object of at least certain embodiments of the
invention to provide beverages and other beverage products having improved
formulations to inhibit fading of colors derived from natural sources and having
improved formulations that inhibit non-enzymatic browning. These and other objects,
features and advantages of the invention or of certain embodiments of the invention
will be apparent to those skilled in the art from the following disclosure and
description of exemplary embodiments.
SUMMARY
[16] In one aspect of the disclosure, a beverage product is provided. The beverage product
includes water, a color derived from a natural source or its synthetic equivalent, and a
compound to inhibit fading of the color derived from a natural source or its synthetic
equivalent. The compound is a hydroxymethane sulfonic acid or ergothioneine.
[17] In another aspect of the disclosure, a beverage product is provided that contains juice
and a hydroxymethane sulfonic acid at an amount effective to inhibit non-enzymatic
browning.
[18] In yet another aspect of the disclosure, a method of inhibiting color change in a
beverage product is provided. Color change is inhibited by adding an effective
amount of a hydroxymethane sulfonic acid to the beverage.
BRIEF DESCRIPTION OF THE FIGURES
[19] The patent or application file contains at least one drawing executed in color. Copies
of this patent or patent application publication with color drawing(s) will be provided
by the Office upon request and payment of the necessary fee.
[20] Figures 1A and IB illustrate the effects of compounds on gardenia blue color stability
in response to light.
[21] Figure 2 illustrates the effects of compounds on gardenia blue color stability in
response to heat.
[22] Figure 3 illustrates the effect of PHMSA and ergothioneine on heat-induced fading of
sweet potato and black carrot color.
[23] Figure 4 illustrates the effect of PHMSA and ergothioneine on light-induced fading of
colors derived from natural sources.
[24] Figure 5 illustrates the effect of chemicals including ergothioneine and sodium
metabisulfite on heat-induced browning in lemon juice.
[25] Figure 6 illustrates inhibition of heat-induced browning in juice by PHMSA and by
tin chloride.
[26] Figure 7 illustrates the effect of compounds on heat-induced browning in orange
juice.
[27] Figure 8 illustrates the sustained efficacy of PHMSA in reducing heat-induced
browning in juice.
DETAILED DESCRIPTION
[28] In an aspect of the disclosure, methods of reducing color changes in response to heat
stress in beverages are provided. In another aspect of the disclosure, methods of
reducing color changes in response to light stress in beverages are provided.
[29] Color changes in beverages can occur through non-enzymatic browning but also
through other mechanisms; for example, colors derived from natural sources can be
used to color beverage products but they can fade in response to heat and/or light
exposure.
[30] It was discovered that stabilized alpha-hydroxymethane sulfonic acids (HMSAs) are
effective for reducing heat- and light-induced browning in beverages.
Advantageously, the HMSAs also reduce heat- and light-induced fading of color
derived from one or more natural sources. HMSAs can therefore be used to promote
color stability in beverages that suffer from non-enzymatic browning and/or color
fading in response to light or heat.
[31] Various HMSAs may be used to promote color stability. Exemplary suitable HMSAs
acids are listed in Table 1.
Table 1
Stabilized alpha-hydroxymethane sulfonic acids are shown by the generic Formula I
below:
I
wherein Ri and R2 form, together with the nitrogen, a pyridine, a quinoline, a
pyrimidine, a tetrahydropyrimidine, an imidazole, a quinoxaline, a riboflavin, or a
pteridine.
[33] 2-pyridyl hydroxymethane sulfonic acid (PHMSA) is particularly suitable for
inhibiting color-change as shown by Formula II:
II
[34] HMSAs inhibit fading of colors derived from natural sources. Colors derived from
natural sources may be added to beverages to enhance their appeal to consumers.
However, these colors can fade in response to heat and/or in response to light. One or
more HMSAs may be added to a beverage to inhibit fading of natural colors in
response to hear and/or light. In some embodiments, a HMSA may be PHMSA. In
other embodiments, a HMSA may be riboflavin hydroxymethane sulfonic acid. More
than one HMSA may be added to a beverage. Each HMSA is added in an effective
amount to inhibit to obtain the desired effect. For example, the amount of HMSA
may be in a range of: about 50 ppm to 500 ppm, about 50 ppm to 250 ppm, or about
50 ppm to 100 ppm. "About," as used herein means plus or minus 10% of the
indicated amount.
[35] PHMSA reduces light-induced fading of colors derived from natural sources. See
Example 1. In response to light, gardenia blue color faded approximately 50% over a
24 hour period (Fig 1A, Row 1 vs Row 6). Of several compounds added to beverage
compositions to test color-protecting effects, PHMSA was the most effective (Fig 1A,
Row 12). Figure IB illustrates these results visually. After 24 hours exposure to
light, the gardenia blue faded substantially (Fig. IB; Bottle C). Bottle A was stored in
the dark to prevent light-induced fading and showed little or no fading. Notably,
however, when PHMSA was added to a beverage composition exposed to light very
little light-induced fading, if any, occurred (Fig. IB; Bottle B).
[36] HMSAs also inhibit heat-induced fading of natural colors. Figure 2 shows the DE
values for a gardenia blue beverage. DE values provide a measure of total color
difference between two samples. DE is calculated from the L, a, and b values, which
indicate lightness, red/green levels, and yellow/blue levels, respectively, and are
determined using a Colorimeter, such as a Hunterlab Colorimeter. DE is calculated
according to the formula:
D E = (D L2 + D a + D b )1 2
[37] Higher DE values indicate a greater degree of color change in a treated beverage
relative to a control beverage. The beverages were heated for a week at 110 °F in the
presence or absence of the indicated compounds. The DE value of 7 for the heattreated
control indicated that the heat treatment induced substantial loss of the
gardenia blue color. Including PHMSA in the beverage reduced heat-induced fading
to a DE value of 4, illustrating the protective effect of HMSAs.
[38] HMSAs protect against heat-induced color-change in other colors derived from
natural sources. See Figure 3. Sweet potato (Fig. 3; hatched line row) and black
carrot (Fig. 3; solid row) colors exposed to 110°F retained less than 30% of their
original color. When PHMSA was added to the beverages, however, at least 75% of
each color, measured by absorbance, was retained.
[39] Similar results were obtained using the same colors derived from natural sources
exposed to light. See Figure 4. Light causes a reduction of over 80% in color for both
sweet potato (hatched line row) and black carrot (solid row) colors. When PHMSA
was added to the beverages, however, at least 75% of each color was retained (Fig. 4).
[40] Ergothioneine has been described as an antioxidant useful for preserving foods and
beverages (See U.S. Pub. No. 2010/0076093) but it has not previously been thought to
protect color from natural sources against fading caused by heat or by light.
Surprisingly, ergothioneine, like HMSAs, can inhibit heat- and light-induced fading
of color from natural sources. See Example 1. Gardenia blue-colored beverages
containing ergothioneine (Fig 1A; Row 7) retained about 90% color when exposed to
light under conditions where a control beverage retained only about 50% color. (Fig
1A, Row 6 "Control 24h"). Similarly, ergothioneine protected color change in colors
derived from natural sources exposed to heat. Both the sweet potato- and black
carrot-colored beverages exhibited improved color stability compared to
ergothioneine-free controls (Fig. 3).
[41] Juice browning results in undesirable beverage color. Advantageously, HMSAs
inhibit juice browning. In an aspect of the disclosure, beverages are provided that
contain at least one HMSA to inhibit juice browning in response to heat-stress.
[42] PHMSA inhibits browning in orange juice. See Example 3. Figure 6 shows that
color change of orange juice incubated at 110 °F was reduced by PHMSA. Higher DE
here indicates increased browning. The lower DE in the beverage containing
PHMSA indicates PHMSA inhibits juice browning in response to heat stress. Figure
7 compares multiple compounds for their effect on browning. While many of the
compounds tested had little or no effect, PHMSA exhibited substantial efficacy.
[43] HMSAs can be used to inhibit browning in beverages at a wide pH range. Example 4
shows that PHMSA maintains reduced browning from pH 2 to pH 7. This pH range
encompasses pH levels used in typical consumer beverages.
[44] The ability of HMSAs to reduce heat-induced browning is sustained over time. See
Example 5 and Figure 8. Orange Juice incubated for three weeks at 110 °F (diamond
line) showed increased browning (DE about 2 after 1 week rising to about 5 after 3
weeks). Tin chloride (square line), a known browning inhibitor, showed good efficacy
until week two when browning more than doubled. In contrast, beverages containing
PHMSA (triangle line) had less browning than control beverages and the PHMSA
exhibited better efficacy than tin chloride at week three.
[45] Color-change inhibition by HMSAs appears to relate to the structure of the stabilized
alpha-hydroxymethane sulfonic acids. In particular, hydrogen bonding of nitrogen to
the hydrogen creates a "six membered" ring that stabilizes the bisulfite addition
product, inhibiting formation of the free bisulfite at low pH. Example 4 establishes
that PHMSA is stable from pH 2 to pH 7, a pH range that encompasses the pH levels
of typical consumable beverages. Because no bisulfite is released through degradation
of PHMSA, the stabilized bisulfite addition product itself is important for browning
inhibition
Tests with additional sulfonic acid compounds further illustrate the importance of the
"six membered" ring. 4-pyridine sulfonic acid and 4-pyridyl ethane sulfonic acid,
which each lack the 2-pyridyl nitrogen moiety, were tested and found not to inhibit
browning (data not shown). Notably, neither compound is capable of forming the
"six membered" ring.
4-pyridyl sulfonic acid 4-pyridyl ethane sulfonic acid
[47] These data establish that the key structural requirement for the functional effects of
HMSAs on color stability is the nitrogen-hydrogen bonding available in all
compounds shown in Table 1, which contributes to stabilization of the "six
membered" ring.
[48] It should be understood that beverages and other beverage products in accordance
with this disclosure may have any of numerous different specific formulations or
constitutions. The formulation of a beverage product in accordance with this
disclosure can vary to a certain extent, depending upon such factors as the product's
intended market segment, its desired nutritional characteristics, flavor profile and the
like. For example, it will generally be an option to add further ingredients to the
formulation of a particular beverage embodiment, including any of the beverage
formulations described below. Additional (i.e., more and/or other) sweeteners may be
added, flavorings, electrolytes, vitamins, fruit juices or other fruit products, tastants,
masking agents and the like, flavor enhancers, and/or carbonation typically can be
added to any such formulations to vary the taste, mouthfeel, nutritional characteristics,
etc.
[49] In certain embodiments of the beverage and other products disclosed here, the color
derived from one or more natural sources is selected from the group consisting of
purple sweet potato, black carrot, purple corn, red beet, carthamus yellow, gardenia
blue, and combinations thereof. The at least one color derived from natural sources
may be present in the beverage product at a concentration of between 150 and 1000
ppm, between 150 and 500 ppm, between 150 and 300 ppm, between 300 ppm and
500 ppm, or between 500 ppm and 1000 ppm. In certain embodiments, ascorbic acid
is also present in the beverage product.
[50] In general, a beverage in accordance with this disclosure typically comprises at least
water, one or more colors derived from natural sources, acidulant and flavoring, and
typically also sweetener. Exemplary flavorings which may be suitable for at least
certain formulations in accordance with this disclosure include herbal flavoring, fruit
flavoring, spice flavorings and others. Carbonation in the form of carbon dioxide may
be added for effervescence. Preservatives can be added if desired, depending upon
the other ingredients, production technique, desired shelf life, etc. Additional and
alternative suitable ingredients will be recognized by those skilled in the art given the
benefit of this disclosure.
[51] The beverage products disclosed here include beverages, i.e., ready to drink liquid
formulations, beverage concentrates and the like. Beverages include, e.g., enhanced
waters, liquid, slurry or solid concentrates, fruit juice-flavored and juice-containing
beverages.
[52] At least certain exemplary embodiments of the beverage concentrates contemplated
are prepared with an initial volume of water to which the additional ingredients are
added. Full strength beverage compositions can be formed from the beverage
concentrate by adding further volumes of water to the concentrate. Typically, for
example, full strength beverages can be prepared from the concentrates by combining
approximately 1 part concentrate with between approximately 3 to approximately 7
parts water. In certain exemplary embodiments the full strength beverage is prepared
by combining 1 part concentrate with 5 parts water. In certain exemplary
embodiments the additional water used to form the full strength beverages is
carbonated water. In certain other embodiments, a full strength beverage is directly
prepared without the formation of a concentrate and subsequent dilution.
[53] Water is a basic ingredient in the beverages disclosed here, typically being the vehicle
or primary liquid portion in which the remaining ingredients are dissolved,
emulsified, suspended or dispersed. Purified water can be used in the manufacture of
certain embodiments of the beverages disclosed here, and water of a standard
beverage quality can be employed in order not to adversely affect beverage taste,
odor, or appearance. The water typically will be clear, colorless, free from
objectionable minerals, tastes and odors, free from organic matter, low in alkalinity
and of acceptable microbiological quality based on industry and government
standards applicable at the time of producing the beverage. In certain typical
embodiments, water is present at a level of from about 80% to about 99.9% by weight
of the beverage. In at least certain exemplary embodiments the water used in
beverages and concentrates disclosed here is "treated water," which refers to water
that has been treated to reduce the total dissolved solids of the water prior to optional
supplementation, e.g., with calcium as disclosed in U.S. Patent No. 7,052,725.
Methods of producing treated water are known to those of ordinary skill in the art and
include deionization, distillation, filtration and reverse osmosis ("r-o"), among others.
The terms "treated water," "purified water,", "demineralized water," "distilled water,"
and "r-o water" are understood to be generally synonymous in this discussion,
referring to water from which substantially all mineral content has been removed,
typically containing no more than about 500 ppm total dissolved solids, e.g. 250 ppm
total dissolved solids.
In certain embodiments, colors derived from natural sources may be used as the only
source of added colorant in beverage compositions, thereby avoiding the use of
synthetic compounds to provide a desired color to the composition. In certain
embodiments, the synthetic equivalents of one or more colors derived from natural
sources are used as the only sources of added colorant in beverage compositions. In
alternate embodiments, colors derived from natural sources, or their synthetic
equivalents, may be employed in combination with synthetic colors. According to
certain embodiments of the beverage products disclosed here, the colors derived from
natural sources comprise one or more colors each derived from natural sources. As
used herein, the term "colors derived from natural sources" includes any and all
extracted products from one or more pigmented biological materials. In certain
exemplary embodiments, the biological materials comprise plant materials. The
coloring provided by colors derived from natural sources may be due to the presence
of flavonoid compounds, such as anthocyanin compounds. Non-limiting examples of
colors derived from natural sources comprising anthocyanins include purple sweet
potato color, black carrot color, purple carrot color, black currant color and blueberry
color. Alternatively, pigmentation can be provided by various other natural
compounds, for example cyclohexene dione dimers such as carthamus yellow color,
colors derived from the reaction of an iridoid and amino acids, such as found in
gardenia blue color. As used herein, "synthetic equivalents" includes any and all
synthetically manufactured compounds having the same structure as a color derived
from a natural source.
[55] The beverages may contain anthocyanin. As disclosed above, anthocyanins are a
class of compounds that may provide pigmentation to colors derived from natural
sources. For example, anthocyanins found in black currants (Ribes nigrum) that
provide pigmentation include 3-diglucoside and 3-rutinoside of cyanidin and
delphinidin. Similarly, blueberries (Vaccinium augustifolium or Vaccinium
corymbosum) typically contain the following anthocyanins that provide pigmentation:
3-glucosides, 3-galactosides, and 3-arabinosides of cyanidin, delphinidin, peonidin,
petunidin, and malvidin.
[56] A blue color derived from natural sources is gardenia blue, which may be formed by
the reaction of an iridoid and an amino acid. For example, hydrolysis of the iridoid
glycoside geniposide with beta-glucosidase, as indicated below, produces the iridoid
genipin. Amino acids, such as glycine, lysine or phenylalanine, will react with the
colorless genipin and form blue pigments.
\ 2 ': <
Further examples of colors derived from natural sources are carthamus yellow and
carthamus red. Carthamus yellow and carthamus red may be derived from safflower
(Carthamus tinctorius), and include cyclohexene dione dimers, which are classified as
chalcone compounds. The chemical structure of carthamus yellow, or carthamin, is
provided below.
Carthamin
[58] Acid used in beverages disclosed here can serve any one or more of several functions,
including, for example, providing antioxidant activity, lending tartness to the taste of
the beverage, enhancing palatability, increasing thirst quenching effect, modifying
sweetness and acting as a mild preservative by providing microbiological stability.
Ascorbic acid, commonly referred to as "vitamin C", is often employed as an
acidulant in beverages to also provide a vitamin to the consumer. Fumaric acid,
maleic acid, mesaconic acid, itaconic acid and/or aconitic acid may be used alone or
in combination with at least one other edible acid in a beverage composition to
provide fading inhibition of colors derived from natural sources, as well as to serve
any of the other purposes of acids in beverages discussed above. In certain
embodiments, between about 30 ppm and 1000 ppm of an unsaturated dicarboxylic
acid may be incorporated into a beverage composition to inhibit fading of colors
derived from natural sources. In certain embodiments of the invention, the effective
amount of one or more unsaturated dicarboxylic acids may be determined either
qualitatively or quantitatively. For example, the effective amount may be an amount
of unsaturated dicarboxylic acid that inhibits color fading such that any change in
color is not readily noticeable to the human eye. Alternatively, the effective amount
may be defined quantitatively as the amount of unsaturated dicarboxylic acid that
prevents the absorbance of a beverage composition at its optimal wavelength
measured using a spectrophotometer from decreasing more than a particular
magnitude, such as 25% of the initial absorbance of the composition at its maximum
wavelength. See also U.S. Patent Application Publication No. 20100151084.
[59] In an embodiment of the invention, fumaric acid may be provided by an acid blend of
fumaric acid, malic acid and tartaric acid, which can be commercially obtained as
Fruitaric® acid, such as the Fruitaric® acid manufactured by Isegen South Africa (Pty)
Ltd, Isipingo, Durban, South Africa. In certain exemplary embodiments, maleic
anhydride may be added to a beverage composition with an acid, and over time the
maleic anhydride will undergo hydrolysis to form maleic acid within the beverage.
Any suitable edible acid may be used to hydrolyze the maleic anhydride, for example
citric acid, malic acid, tartaric acid, phosphoric acid, ascorbic acid, lactic acid, formic
acid, fumaric acid, gluconic acid, succinic acid and/or adipic acid.
[60] The acid can be used in solution form, for example, and in an amount sufficient to
provide the desired pH of the beverage. Typically, for example, the one or more acids
of the acidulant are used in amount, collectively, of from about 0.01% to about 1.0%
by weight of the beverage, e.g., from about 0.05% to about 0.5% by weight of the
beverage, such as 0.1% to 0.25% by weight of the beverage, depending upon the
acidulant used, desired pH, other ingredients used, etc. In certain embodiments of the
invention, all of the acid included in a beverage composition may be provided by one
or more alpha,beta-unsaturated dicarboxylic acids.
[61] The pH of at least certain exemplary embodiments of the beverages disclosed here
can be a value within the range of 2.5 to 4.6. The acid in certain exemplary
embodiments can enhance beverage flavor. Too much acid can impair the beverage
flavor and result in sourness or other off-taste, while too little acid can make the
beverage taste flat and reduce microbiological safety of the product. It will be within
the ability of those skilled in the art, given the benefit of this disclosure, to select a
suitable acid or combination of acids and the amounts of such acids for the acidulant
component of any particular embodiment of the beverage products disclosed here.
[62] Sweeteners suitable for use in various embodiments of the beverages disclosed here
include nutritive and non-nutritive, natural and artificial or synthetic sweeteners.
Suitable non-nutritive sweeteners and combinations of sweeteners are selected for the
desired nutritional characteristics, taste profile for the beverage, mouthfeel and other
organoleptic factors. Non-nutritive sweeteners suitable for at least certain exemplary
embodiments include, but are not limited to, for example, peptide based sweeteners,
e.g., aspartame, neotame, and alitame, and non-peptide based sweeteners, for
example, sodium saccharin, calcium saccharin, acesulfame potassium, sodium
cyclamate, calcium cyclamate, neohesperidin dihydrochalcone, and sucralose. In
certain embodiments the sweetener comprises acesulfame potassium. Other nonnutritive
sweeteners suitable for at least certain exemplary embodiments include, for
example, sorbitol, mannitol, xylitol, glycyrrhizin, D -tagatose, erythritol, mesoerythritol,
maltitol, maltose, lactose, fructo-oligosaccharides, Lo Han Guo powder,
xylose, arabinose, isomalt, lactitol, maltitol, trehalose, and ribose, and protein
sweeteners such as thaumatin, monellin, brazzein, L-alanine and glycine, related
compounds, and mixtures of any of them. Lo Han Guo, rebaudioside A, and monatin
and related compounds are natural non-nutritive potent sweeteners . Suitable
sweeteners also include rhamnose and sweetener fractions of stevia.
[63] In at least certain exemplary embodiments of the beverages disclosed here, the
sweetener component can include nutritive, natural crystalline or liquid sweeteners
such as sucrose, liquid sucrose, fructose, liquid fructose, glucose, liquid glucose,
glucose-fructose syrup from natural sources such as apple, chicory, honey, etc., e.g.,
high fructose corn syrup, invert sugar, maple syrup, maple sugar, honey, brown sugar
molasses, e.g., cane molasses, such as first molasses, second molasses, blackstrap
molasses, and sugar beet molasses, sorghum syrup, Lo Han Guo juice concentrate,
agave and/or others. Such sweeteners are present in at least certain exemplary
embodiments in an amount of from about 0.1% to about 20% by weight of the
beverage, such as from about 6% to about 16% by weight, depending upon the desired
level of sweetness for the beverage. To achieve desired beverage uniformity, texture
and taste, in certain exemplary embodiments of the natural beverage products
disclosed here, standardized liquid sugars as are commonly employed in the beverage
industry can be used. Typically such standardized sweeteners are free of traces of
nonsugar solids which could adversely affect the flavor, color or consistency of the
beverage.
[64] Non-nutritive, high potency sweeteners typically are employed at a level of
milligrams per fluid ounce of beverage, according to their sweetening power, any
applicable regulatory provisions of the country where the beverage is to be marketed,
the desired level of sweetness of the beverage, etc. It will be within the ability of
those skilled in the art, given the benefit of this disclosure, to select suitable additional
or alternative sweeteners for use in various embodiments of the beverage products
disclosed here.
[65] Preservatives may be used in certain embodiments of the beverages disclosed here.
That is, certain exemplary embodiments contain an optional dissolved preservative
system. Solutions with a pH below 4 and especially those below 3 typically are
"microstable," i.e., they resist growth of microorganisms, and so are suitable for
longer term storage prior to consumption without the need for further preservatives.
However, an additional preservative system can be used if desired. If a preservative
system is used, it can be added to the beverage product at any suitable time during
production, e.g., in some cases prior to the addition of the sweetener. As used here,
the terms "preservation system" or "preservatives" include all suitable preservatives
approved for use in food and beverage compositions, including, without limitation,
such known chemical preservatives as benzoic acid, benzoates, e.g., sodium, calcium,
and potassium benzoate, sorbates, e.g., sodium, calcium, and potassium sorbate,
citrates, e.g., sodium citrate and potassium citrate, polyphosphates, e.g., sodium
hexametaphosphate (SHMP), lauryl arginate ester, cinnamic acid, e.g., sodium and
potassium cinnamates, polylysine, and antimicrobial essential oils, dimethyl
dicarbonate, and mixtures thereof, and antioxidants such as ascorbic acid, EDTA,
BHA, BHT, TBHQ, EMIQ, dehydroacetic acid, ethoxyquin, heptylparaben, and
combinations thereof.
[66] Preservatives can be used in amounts not exceeding mandated maximum levels under
applicable laws and regulations. The level of preservative used typically is adjusted
according to the planned final product pH, as well as an evaluation of the
microbiological spoilage potential of the particular beverage formulation. The
maximum level employed typically is about 0.05% by weight of the beverage. It will
be within the ability of those skilled in the art, given the benefit of this disclosure, to
select a suitable preservative or combination of preservatives for beverages according
to this disclosure. In certain embodiments of the invention, benzoic acid or its salts
(benzoates) may be employed as preservatives in the beverage products.
[67] Other methods of beverage preservation suitable for at least certain exemplary
embodiments of the beverage products disclosed here include, e.g., aseptic packaging
and/or heat treatment or thermal processing steps, such as hot filling, tunnel
pasteurization, and non-thermal processing. Such steps can be used to reduce yeast,
mold and microbial growth in the beverage products. For example, U.S. Patent No.
4,830,862 to Braun et al. discloses the use of pasteurization in the production of fruit
juice beverages as well as the use of suitable preservatives in carbonated beverages.
U.S. Patent No. 4,925,686 to Kastin discloses a heat-pasteurized freezable fruit juice
composition which contains sodium benzoate and potassium sorbate. In general, heat
treatment includes hot fill methods typically using high temperatures for a short time,
e.g., about 190° F for 10 seconds, tunnel pasteurization methods typically using lower
temperatures for a longer time, e.g., about 160° F for 10-15 minutes, and retort
methods typically using, e.g., about 250° F for 3-5 minutes at elevated pressure, i.e.,
at pressure above 1 atmosphere.
[68] The beverage products disclosed here optionally contain a flavor composition, for
example, natural and synthetic fruit flavors, botanical flavors, other flavors, and
mixtures thereof. As used here, the term "fruit flavor" refers generally to those
flavors derived from the edible reproductive part of a seed plant. Included are both
those wherein a sweet pulp is associated with the seed, e.g., banana, tomato, cranberry
and the like, and those having a small, fleshy berry. The term berry also is used here
to include aggregate fruits, i.e., not "true" berries, but that are commonly accepted as
a berry. Also included within the term "fruit flavor" are synthetically prepared flavors
made to simulate fruit flavors derived from natural sources. Examples of suitable
fruit or berry sources include whole berries or portions thereof, berry juice, berry juice
concentrates, berry purees and blends thereof, dried berry powders, dried berry juice
powders, and the like.
[69] Exemplary fruit flavors include the citrus flavors, e.g., orange, lemon, lime and
grapefruit, and such flavors as apple, pomegranate, grape, cherry, and pineapple
flavors and the like, and mixtures thereof. In certain exemplary embodiments the
beverage concentrates and beverages comprise a fruit flavor component, e.g., a juice
concentrate or juice. As used here, the term "botanical flavor" refers to flavors
derived from parts of a plant other than the fruit. As such, botanical flavors can
include those flavors derived from essential oils and extracts of nuts, bark, roots and
leaves. Also included within the term "botanical flavor" are synthetically prepared
flavors made to simulate botanical flavors derived from natural sources. Examples of
such flavors include cola flavors, tea flavors, and the like, and mixtures thereof. The
flavor component can further comprise a blend of the above-mentioned flavors. The
particular amount of the flavor component useful for imparting flavor characteristics
to the beverages of the present invention will depend upon the flavor(s) selected, the
flavor impression desired, and the form of the flavor component. Those skilled in the
art, given the benefit of this disclosure, will be readily able to determine the amount
of any particular flavor component(s) used to achieve the desired flavor impression.
Juices suitable for use in at least certain exemplary embodiments of the beverage
products disclosed here include, e.g., fruit, vegetable and berry juices. Juices can be
employed in the present invention in the form of a concentrate, puree, single-strength
juice, or other suitable forms. The term "juice" as used here includes single-strength
fruit, berry, or vegetable juice, as well as concentrates, purees, milks, and other forms.
Multiple different fruit, vegetable and/or berry juices can be combined, optionally
along with other flavorings, to generate a beverage having the desired flavor.
Examples of suitable juice sources include plum, prune, date, currant, fig, grape, red
grape, sweet potato, raisin, cranberry, pineapple, peach, banana, apple, pear, guava,
apricot, Saskatoon berry, blueberry, plains berry, prairie berry, mulberry, elderberry,
Barbados cherry (acerola cherry), choke cherry, date, coconut, olive, raspberry,
strawberry, huckleberry, loganberry, currant, dewberry, boysenberry, kiwi, cherry,
blackberry, quince, buckthorn, passion fruit, sloe, rowan, gooseberry, pomegranate,
persimmon, mango, rhubarb, papaya, lychee, lemon, orange, lime, tangerine,
mandarin orange, tangelo, and pomelo and grapefruit, etc. Numerous additional and
alternative juices suitable for use in at least certain exemplary embodiments will be
apparent to those skilled in the art given the benefit of this disclosure. In the
beverages of the present invention employing juice, juice may be used, for example,
at a level of at least about 0.2% by weight of the beverage. In certain exemplary
embodiments juice is employed at a level of from about 0.2% to about 40% by weight
of the beverage. Typically, juice can be used, if at all, in an amount of from about 1%
to about 20% by weight.
[71] Other flavorings suitable for use in at least certain exemplary embodiments of the
beverage products disclosed here include, e.g., spice flavorings, such as cassia, clove,
cinnamon, pepper, ginger, vanilla spice flavorings, cardamom, coriander, root beer,
sassafras, ginseng, and others. Numerous additional and alternative flavorings
suitable for use in at least certain exemplary embodiments will be apparent to those
skilled in the art given the benefit of this disclosure. Flavorings can be in the form of
an extract, oleoresin, juice concentrate, bottler's base, or other forms known in the art.
In at least certain exemplary embodiments, such spice or other flavors complement
that of a juice or juice combination.
[72] The one or more flavorings can be used in the form of an emulsion. A flavoring
emulsion can be prepared by mixing some or all of the flavorings together, optionally
together with other ingredients of the beverage, and an emulsifying agent. The
emulsifying agent may be added with or after the flavorings mixed together. In
certain exemplary embodiments the emulsifying agent is water-soluble. Exemplary
suitable emulsifying agents include gum acacia, modified starch,
carboxymethylcellulose, gum tragacanth, gum ghatti and other suitable gums.
Additional suitable emulsifying agents will be apparent to those skilled in the art of
beverage formulations, given the benefit of this disclosure. The emulsifier in
exemplary embodiments comprises greater than about 3% of the mixture of flavorings
and emulsifier. In certain exemplary embodiments the emulsifier is from about 5% to
about 30% of the mixture.
[73] Carbon dioxide can be used to provide effervescence to certain exemplary
embodiments of the beverages disclosed here. Any of the techniques and carbonating
equipment known in the art for carbonating beverages can be employed. Carbon
dioxide can enhance the beverage taste and appearance and can aid in safeguarding
the beverage purity by inhibiting and destroying objectionable bacteria. In certain
embodiments, for example, the beverage has a CO2 level up to about 7.0 volumes
carbon dioxide. Typical embodiments may have, for example, from about 0.5 to 5.0
volumes of carbon dioxide. As used here and independent claims, one volume of
carbon dioxide is defined as the amount of carbon dioxide absorbed by any given
quantity of water at 60° F (16° C) temperature and atmospheric pressure. A volume
of gas occupies the same space as does the water by which it is absorbed. The carbon
dioxide content can be selected by those skilled in the art based on the desired level of
effervescence and the impact of the carbon dioxide on the taste or mouthfeel of the
beverage. The carbonation can be natural or synthetic.
[74] The beverage concentrates and beverages disclosed here may contain additional
ingredients, including, generally, any of those typically found in beverage
formulations. These additional ingredients, for example, can typically be added to a
stabilized beverage concentrate. Examples of such additional ingredients include, but
are not limited to, caffeine, caramel and other coloring agents or dyes, antifoaming
agents, gums, emulsifiers, tea solids, phytochemicals, cloud components, and mineral
and non-mineral nutritional supplements. Examples of non-mineral nutritional
supplement ingredients are known to those of ordinary skill in the art and include, for
example, antioxidants and vitamins, including Vitamins A, D, E (tocopherol), C
(ascorbic acid), Bi (thiamine), B2 (riboflavin), B (nicotinamide), B4 (adenine), B
(pantothenic acid, calcium), B (pyridoxine H ), Bi2 (cyanocobalamin), and Ki
(phylloquinone), niacin, folic acid, biotin, and combinations thereof . The optional
non-mineral nutritional supplements are typically present in amounts generally
accepted under good manufacturing practices. Exemplary amounts are between about
1% and about 100% RDV, where such RDV are established. In certain exemplary
embodiments the non-mineral nutritional supplement ingredient(s) are present in an
amount of from about 5% to about 20% RDV, where established.
EXAMPLE 1
PHMSA Prevents Gardenia Blue Fading Induced by Heat and Light
[75] PHMSA' s ability to inhibit fading of gardenia blue, a colors derived from natural
source, was tested as follows. Beverages were prepared according to the ingredients
listed in Table 2 and shaken until all compounds were dissolved. Table 3 indicates
compounds added to each beverage for the light stress test. Table 4 indicates
compounds added to each beverage for the heat stress test. For light stress, the
beverage compositions were exposed to 0.35 W/m2 at 86 °F for 24h using a
Weatherometer. For heat stress, the beverage was stored at 110 °F for 1 week. Light
and heat effects were evaluated by visual observation, as well as color measurement
using a spectrophotometer and colorimeter. Absorbance was determined at 595 nm
(maximum abs) using a spectrophotometer Shimadzu UV-1800. Color (L, a, and, b
parameters) was determined using a HunterLab ColorQuest XE colorimeter in total
transmittance mode. pH was determined using a Metrohm 827 ph lab were measured
to the selected samples.
[76] The results of the light-stress test are shown in Figure 1A. The degree of color of the
"control Oh" sample, Row 1, was used as the 100% value. After 24 hours exposure to
light, ony 44.31% color remaining (Row 6 "Control 24 h" sample). The beverage
containing PHMSA showed the highest color remaining (120.36 %) of the samples
exposed to light for 24 hours, indicating that color is brighter with PHMSA. These
data demonstrate that 333 ppm 2-pyridylhydroxymethanesulfonic acid reduces
gardenia blue color fading due to light.
[77] The data also demonstrates the ability of ascorbic acid to drive fading of color from a
natural source. The beverages in Row 2 and Row 6 contained the same ingredients
except that the Row 2 beverage lacked ascorbic acid. Both were exposed to light for
24 hours. The Row 6 beverage faded to a greater extent, showing that ascorbic acid
(vitamin C) promotes gardenia blue fading. Thus, while the presence of vitamin C is
desirable from a nutritional standpoint, its ability to promote color change creates a
problem with consumer uptake. The ability of HMSAs to reduce light-induced fading
driven by vitamin C is therefore particularly useful.
[78] Visual observation of the samples confirmed the effect of PHMSA. Figure IB. The
beverage containing PHMSA (Bottle B; 333 ppm) showed greater color intensity than
control sample without light exposure (Bottle A) and much more color intensity than
a sample without compound when exposed to light for 24h (Bottle C).
[79] PHMSA was also effective in preventing fading in response to heat-stress. Figure 2
discloses DE values for beverage compositions containing gardenia blue and various
compounds. Heating beverage compositions containing gardenia blue at 110 °F for
24 hours caused fading of the gardenia blue color (compare row 1 "Control Oh" vs.
row 5 "Control 24h"). PHMSA inhibited heat-induced color change (compare row 1
"Control Oh" vs. row 11 "PHMSA"). These data established the ability of HMSAs to
inhibit fading of colors from natural sources in response to heat stress.
[80]
Table 2
Table 3
Com ounds added to bevera e com osition to test color stabilit in res onse to li ht
Table 4
Compounds added to beverage composition to test color stability in response to heat
umar c ac ppm
EXAMPLE 2
PHMSA and Ergothioneine Reduce Heat- and Light-Induced Fading in a Variety of
Colors Derived from Natural Sources
[81] To establish that HMSAs protect against fading in multiple colors from natural
sources, beverage compositions having sweet potato or black carrot colors were
tested.
[82] For light-induced fading, beverages were exposed to light for 24 h (Weatherometer,
86 °F, 0.35 W/m2; Fig.4 "control light" vs "control dark"). For heat-induced fading,
beverages were heated at 110 °F for 1 week (Fig. 3 "control 110 °F vs "control 40
°F").
[83] Figure 3 shows that exposure to 110 °F heat reduced absorbance to 26.72% (sweet
potato) and 26.28% (black carrot). In the presence of PHMSA, absorbance was
84.13% (sweet potato) and 81.41% (black carrot), illustrating PHMSA's ability to
reduce heat-induced fading. Adding ergothioneine also reduced fading. Absorbance
was 68.78% (sweet potato) and 93.91% (black carrot), demonstrating that
ergothioneine provides substantial protection from heat-induced fading.
[84] Figure 2 shows that, as with sweet potato and black carrot, ergothioneine inhibits
heat-induced fading of gardenia blue. Exposing beverages containing gardenia blue
to 110 °F heat for 24 h increases fading, as measured by DE, from about 4 to almost 8.
Beverages containing ergothioneine (333 ppm) had a DE of less than 3 establishing
that ergothioneine effectively reduces heat-induced fading of color derived from
natural sources.
[85] Figure 4 shows that PHMSA and ergothioneine protect against light-induced fading of
colors from natural sources. Light treatment reduced absorbance to 12.43% (sweet
potato) and 14.42% (black carrot). In the presence of ergothioneine, however,
absorbance was 84.66% (sweet potato) and 42.63% (black carrot), demonstrating
substantial protection from light-induced fading. Similarly, in the presence of
PHMSA, absorbance was 82.54% (sweet potato) and 75.32% (black carrot),
illustrating PHMSA's ability to inhibit light-induced fading of color derived from
natural sources.
[86] Figure 1A shows that ergothioneine inhibits light-induced fading of gardenia blue.
The beverage compositions were exposed to 0.35 W/m2 at 86 °F for 24h using a
Weatherometer. After 24 hours exposure to light, less than 50% color remained
(compare row 1 vs. row 6). Beverages containing ergothioneine (333 ppm) retained
about 90% of the color (compare row 1 vs. row 7) establishing that ergothioneine
reduces light-induced fading of color derived from natural sources.
EXAMPLE 3
PHMSA Reduces Heat-Induced Non-Enzymatic Browning in Juice
[87] Orange Juice beverages were prepared using commercially processed orange juice
concentrate (65.5-66.5 Brix; Citrosuco). The pH values of the concentrate ranged
from 3.5-4.3. A typical high ratio low oil OJ concentrate was used which was diluted
with treated water to 12.5 brix to make 100% single strength orange juice. Citrus
juice concentrates were stored in darkness and frozen until reconstituted to single
strength orange juice. The concentrate was diluted into a single strength orange juice
at 12.5 brix using treated water.
[88] The juice beverage was pasteurized at 95 °C for 6-8 seconds and filled into 15.2 Oz
(450 mL) PET bottles with oxygen barrier properties and oxygen scavenging ability
(Graham Packaging Company). The oxygen barrier properties reduce the incidence of
bisulfite degradation to sulfate. Bisulfite and tin (II) chloride, known browning
inhibitors, were used as positive controls.
[89] Bottles containing the juice beverage were treated with different browning inhibitors
as indicated in Table 3, pasteurized and stored at 110°F in the dark for 3-4 weeks.
Controls were stored at 40°F and 110°F without inhibitor treatment. Samples were
prepared in duplicate. Before and after the study, the control samples at 40°F and
110°F were analyzed for: Brix, pH, dissolved oxygen, and HMF production.
[90] In lemon juice, little change in Brix occurred after exposure to heat. After 3 weeks at
110 °F Brix, measured by refractometer, was 14 versus 13.8 for the 3-week control at
40 °F. Notably, HMF increased substantially due to heat. Control at 0 weeks at 40 °F
showed 226 ppb. After 3 weeks at 40 °F, HMF had risen to 965.9 ppb. But after
three weeks at 110 °F HMF was 34971.4 ppb.
[91] Results in orange juice were similar. After 3 weeks at 110 °F Brix, measured by
refractometer, was 12.9 versus 12.76 for the 3-week control at 40 °F. Again, HMF
increased substantially due to heat. Control at 0 weeks at 40 °F showed 485 ppb
HMF. After 3 weeks at 40 °F, HMF had risen to 550.3 ppb. After three weeks at 110
°F, however, HMF was 9069.3 ppb. Notably, Vitamin C levels declined from 457.78
mg/L in the 3-week control at 40 °F to 323.62 mg/L.
[92] Amino acid analysis (Table 5) showed that proline and lysine were the only amino
acids depleted, indicating that they were being consumed in a Maillard reaction and
contributing to browning.
Table 5
[93] Juice color change in response to the heat-stress was assessed using two separate
approaches. First, L*, a, and b values were measured using a Hunter Lab Colorimeter
values according to the CIE-Lab Color Scale. Higher L* value means a lighter color
of juice. In addition to the L* measurement, a panel of four non-color blind scientist
visually assessed the beverages and confirmed the L* value results.
[94] Results from one study are shown in Table 6. Heating the beverage at 110 °F reduced
lightness (L*) from 44.63, as determined for control beverage stored at 40 °F, to
41.27, indicating increased browning. Beverage containing sodium bisulfite had a
lightness value of 41.91. Beverage containing PHMSA had a lightness value of
42.45. Kojic acid was found to be ineffective in inhibiting browning, in contrast to
previous results. See Mohamad et al. 2010. These data established that PHMSA is
effective at inhibiting browning.
Table 6
EXAMPLE 4
PHMSA inhibits Non-Enzymatic Juice Browning over a Broad pH Range
Sodium bisulfite inhibits browning by releasing free bisulfite at low pH levels. One
possible mechanism for HMSA function was release of bisulfite from the HMSAs.
To investigate the mechanism, PHMSA pH stability was tested by measuring
picolinic aldehyde (PA) formation. PA is a precursor aldehyde of PHMSA and is
formed when PHMSA decomposes. Because chromatographic analysis by HPLC is
extremely complex in orange juice, PHMSA decomposition was assessed in heated
beverage models.
[96] Beverage model compositions were prepared by dissolving PHMSA (80mg) in 50mL
of four different buffers. The compositions were prepared using suitable acids, such
as citric acid and phosphoric acid to provide solutions at pH 2, 4, 7, and 9, which were
heated at 110°F for 3 weeks. PA formation was evaluated by HPLC on RPC18 with
water and 0.1% acetic acid as eluent. HPLC conditions were optimized for detection
of PHMSA and picolinic aldehyde formation by UV monitoring at 254nm. A
picolinic aldehyde standard was used as a reference to measure conversion of
PHMSA to the aldehyde.
[97] The retention time of PHMSA in the HPLC was 4.13 minutes (80mg/50mL). The
retention time of picolinic aldehyde was 10.13 minutes (40mg/50mL). The PA
(picolinic aldehyde) concentration was used to approximate 100% of aldehyde content
per mole degradation of the PHMSA.
[98] We detected no picolinic aldehyde in the beverage models at pH 2, 4, or 7, indicating
that PHMSA is stable at these pH levels (data not shown). At pH 9, however, a small
amount of picolinic aldehyde was detected, indicating that PHMSA remains
substantially stable even up to about pH 9. These data suggest that PHMSA remains
in the addition product state up to at pH 7. PHMSA is therefore useful for browning
inhibition and preventing fading of colors from natural sources or their synthetic
equivalents from pH 2 to pH 7.
[99] Further, the data implies that PHMSA operates in a mechanism unlike that of
bisulfite. At acid pH, sodium bisulfite releases free bisulfite, which inhibits
browning. If fully dissociated, PHMSA (MW 189.2 grams/mole) provides 56.6%
aldehyde and 43.3% of bisulfite. Thus, assuming complete dissociation, adding
75mg of PHMSA per bottle would supply about 32.5 mg of bisulfite. This amount of
bisulfite would offer superb browning inhibition. However, because PHMSA did not
release bisulfite at acid or neutral pH, PHMSA must inhibit color fading and
browning by a different mechanism. For example, PHMSA may be absorbing light or
acting as a radical scavenger, a metal chelator, or an oxidation sponge antioxidant.
EXAMPLE 5
PHMSA Protects Against Heat-Induce Browning Over Sustained Periods
[100] Experiments were performed to assess how long PHMSA protects against color
change. PHMSA or tin chloride was each added to a juice beverage. The beverages
were then incubated at 110 °F for extended periods of time. DE, indicating increased
browning, was measured at 1, 2, and 3 weeks. As shown in Table 7 and represented
graphically in Figure 8, PHMSA had a sustained inhibitory effect on browning.
Notably, while tin chloride was effective in the short term, it appeared to become less
effective during extended heating, resulting in an increase in DE from 2.00 to 4.54
between the second and third week. In contrast, while PHMSA showed less effective
browning inhibition after one week compared to tin chloride, PHMSA exhibited
greater efficacy at week 3.
Table 7
Effect of Tin Chloride and PHMSA on Brownin at 110 °F for extended eriods
EXAMPLE 6
Ergothioneine Reduces Heat-Stress-Induced Non-Enzymatic Browning in Lemon
Juice
[101] Ergothioneine reduces lemon juice browning to a similar extent as sodium bisulfite.
Lemon juice compositions were prepared containing the compounds listed in table 8
then exposed to 110 °F heat. Control juice compositions with no compounds added
were incubated at 110 °F and at 40 °F. The heat stress caused a decrease in lemon
juice color lightness (L*) from 95.96 to 94.28. Ergothioneine inhibited the heatinduced
decrease. Color lightness was 95.69 and 95.36 when 25 ppm and 50 ppm
Ergothioneine were included in the juice, respectively. This degree of protection is
similar to sodium bisulfite. Adding sodium bisulfite at 16.7 ppm or at 8.5 ppm,
provided lightness values of 95.65 and 95.37, respectively. Ergothioneine thus offers
protection against browning to the same extent as sodium bisulfite but does not suffer
from the possible allergen issues associated with sodium bisulfite use.
Table 8
Ergothioneine protects against heat-induced browning in lemon juice
[102] Similar data is presented in Figure 5. Figure 5 shows the b* values for lemon juice
beverages. Lower b* value indicates less browning. Heat treatment of the lemon
juice increased browning (Compare "control 110 °F" vs. "control 40 °F").
Ergothioneine was effective in reducing heat-induced browning.
[103] Orange juice beverages containing compounds as listed in Table 9 were heated at 110
°F for 3 weeks. An unheated control was maintained at 40 °F. The heat stress at 110
°F caused a decrease in color lightness from 40.16 to 36.63. Positive controls, tin
chloride and sodium bisulfite, both maintained juice lightness at 39.32. PHMSA and
ergothioneine maintained juice lightness at 38.68 and 39.01, respectively. In contrast
to the results obtained with ergothioneine and PHMSA, dehydroascorbic, and
hypotaurine were not effective in preventing heat-induced browning.
Table 9
Juice color for bevera es containin various com ounds heated at 110 °F
[104] Calculations from two separate heat stressed-orange juice trials, shown in table 10,
established the reproducibility of browning inhibition by PHMSA and by
ergothioneine.
Table 10
DE values from two Oran e uice trials.
[105] Figure 6 illustrates data for two additional trials. PHMSA reduces color change in
orange juice, as measured by DE, compared to the control heated at 110°F.
[106] While particular embodiments have been described and illustrated, it should be
understood that the invention is not limited thereto since modifications may be made
by persons skilled in the art. The present application contemplates any and all
modifications that fall within the spirit and scope of the underlying invention
disclosed and claimed herein. The contents of each of the cited journal articles,
patents, and published patent applications are hereby incorporated by reference as if
set forth fully herein.
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WHAT IS CLAIMED IS:
A beverage product comprising:
water;
a color derived from a natural source or its synthetic equivalent; and
a compound selected from a hydroxymethane sulfonic acid (HMSA)
ergothioneine to inhibit fading of the color derived from a natural source
synthetic equivalent.
2. The beverage product of claim 1 wherein the compound is the HMSA and the HMSA
is of Formula I :
I
wherein Ri and R2, together with the nitrogen, form a pyridine, a quinoline, a
pyrimidine, a tetrahydropyrimidine, an imidazole, a quinoxaline, a riboflavin, or a
pteridine.
3. The beverage product of claim 2 wherein the HMSA is 2-pyridyl hydroxymethane
sulfonic acid.
4. The beverage product of any one of claims 1-3 wherein the natural source is selected
from the group consisting of: purple sweet potato, black carrot, purple carrot, black
currant, blueberry, carthamus yellow, gardenia blue, and combinations thereof.
5. The beverage product of any one of claims 1-4 wherein the compound is present at a
concentration of between about 30 ppm and about 1000 ppm.
6. The beverage product of any one of claims 1, 4, or 5 wherein the compound is
ergothioneine.
7. A beverage product comprising:
a juice, and an inhibitor in an effective amount to inhibit non-enzymatic browning, the
inhibitor comprising a hydroxymethane sulfonic acid (HMSA).
8. The beverage product of claim 7 wherein the HMSA is of Formula I :
I
wherein Ri and R2, together with the nitrogen, form a pyridine, a quinoline, a
pyrimidine, a tetrahydropyrimidine, an imidazole, a quinoxaline, a riboflavin, or a
pteridine.
9. The beverage product of claim 8 wherein the HMSA is a pyridyl hydroxymethane
sulfonic acid.
10. The beverage product of any one of claims 7-9 wherein the non-enzymatic browning
is light-induced or heat-induced.
11. The beverage product of any of claims 7-10, wherein the compound is present at a
concentration of between about 30 ppm and about 1000 ppm.
13. The beverage product of any of claims 7-11, wherein the juice is a fruit juice.
14. A method of inhibiting color change in a beverage product comprising adding an
effective amount of a hydroxymethane sulfonic acid (HMSA) to a beverage.
15. The method of claim 14 wherein the color change is heat-induced fading, lightinduced
fading, or non-enzymatic browning.
16. The method of claim 14 wherein the HMSA is of Formula I :
I
wherein Ri and R2, together with the nitrogen, form a pyridine, a quinoline, a
pyrimidine, a tetrahydropyrimidine, an imidazole, a quinoxaline, a riboflavin, or a
pteridine.
The method of claim 16 wherein the hydroxymethane sulfonic acid is a pyridyl
hydroxymethane sulfonic acid.