U.S. patent application number 15/305299 was filed with the patent office on 2017-02-09 for methods of making modified alcohol containing products.
This patent application is currently assigned to REGENTS OF THE UNIVERSITY OF MINNESOTA. The applicant listed for this patent is REGENTS OF THE UNIVERSITY OF MINNESOTA. Invention is credited to Smaro Kokkinidou, Devin Grant Peterson.
Application Number | 20170036974 15/305299 |
Document ID | / |
Family ID | 54333101 |
Filed Date | 2017-02-09 |
United States Patent
Application |
20170036974 |
Kind Code |
A1 |
Peterson; Devin Grant ; et
al. |
February 9, 2017 |
METHODS OF MAKING MODIFIED ALCOHOL CONTAINING PRODUCTS
Abstract
Certain embodiments of the invention provide a method of
preparing a modified distilled alcoholic spirit, comprising
contacting a corresponding starting distilled alcoholic spirit with
a base under conditions that cause at least one free carbonyl
compound in the starting distilled alcoholic spirit to be reduced,
to provide the modified distilled alcoholic spirit that has at an
alcohol by volume (ABV) of at least 15%. Certain embodiments also
provide a modified distilled alcoholic spirit prepared by the
methods described herein.
Inventors: |
Peterson; Devin Grant;
(Minneapolis, MN) ; Kokkinidou; Smaro;
(Minneapolis, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
REGENTS OF THE UNIVERSITY OF MINNESOTA |
Minneapolis |
MN |
US |
|
|
Assignee: |
REGENTS OF THE UNIVERSITY OF
MINNESOTA
Minneapolis
MN
|
Family ID: |
54333101 |
Appl. No.: |
15/305299 |
Filed: |
April 21, 2015 |
PCT Filed: |
April 21, 2015 |
PCT NO: |
PCT/US15/26929 |
371 Date: |
October 19, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61982228 |
Apr 21, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61K 31/045 20130101;
C12H 1/0408 20130101; C12H 1/063 20130101; A61K 8/34 20130101; C07C
29/132 20130101; C12H 1/0424 20130101; A61Q 11/00 20130101 |
International
Class: |
C07C 29/132 20060101
C07C029/132; A61Q 11/00 20060101 A61Q011/00; C12H 1/044 20060101
C12H001/044; C12H 1/056 20060101 C12H001/056; C12H 1/07 20060101
C12H001/07; A61K 8/34 20060101 A61K008/34; A61K 31/045 20060101
A61K031/045 |
Claims
1. A method of preparing a modified distilled alcoholic spirit,
comprising contacting a corresponding starting distilled alcoholic
spirit with a base under conditions that cause at least one free
carbonyl compound in the starting distilled alcoholic spirit to be
reduced, to provide the modified distilled alcoholic spirit that
has an alcohol by volume (ABV) of at least about 15%.
2. A method of preparing a modified distilled alcoholic spirit,
comprising contacting a corresponding starting distilled alcoholic
spirit with a base under conditions that cause the total of free
carbonyl compounds in the starting distilled alcoholic spirit to be
reduced, to provide the modified distilled alcoholic spirit that
has an alcohol by volume (ABV) of at least about 15%.
3. The method of claim 1 or 2, wherein the modified distilled
alcoholic spirit is whiskey, rum, brandy, tequila, soju, gin or
baiju.
4. The method of any one of claims 1-3, wherein the pH of the
starting distilled alcoholic spirit is about 2.5 to about 4.5.
5. The method of claim 4, wherein the pH of the starting distilled
alcoholic spirit is about 3 to about 4.4.
6. The method of any one of claims 1-5, wherein the pH of the
modified distilled alcoholic spirit is about 5 to about 12.
7. The method of claim 6, wherein the pH of the modified distilled
alcoholic spirit is about 6 to about 8.
8. The method of any one of claims 1-7, wherein the base is a food
grade additive.
9. The method of any one of claims 1-8, wherein the base is sodium
bicarbonate, sodium carbonate, sodium hydroxide, potassium
hydroxide, potassium carbonate or potassium bicarbonate.
10. The method of any one of claims 1-9, wherein the base is a
solid.
11. The method of any one of claims 1 and 3-10, wherein the at
least one free carbonyl compound is reduced by at least about 20%
by weight.
12. The method of any one of claims 1 and 3-10, wherein the at
least one free carbonyl compound is reduced by at least about 40%
by weight.
13. The method of any one of claims 1 and 3-10, wherein the at
least one free carbonyl compound is reduced by at least about 80%
by weight.
14. The method of any one of claims 2-10, wherein the total of the
free carbonyl compounds is reduced by at least about 20% by
weight.
15. The method of any one of claims 2-10, wherein the total of the
free carbonyl compounds is reduced by at least about 40% by
weight.
16. The method of any one of claims 2-10, wherein the total of the
free carbonyl compounds is reduced by at least about 80% by
weight.
17. The method of any one of claims 1-16, wherein at least one free
carbonyl compound is an aldehyde.
18. The method of claim 17, wherein the aldehyde is selected from
acetaldehyde, 2-methylbutanal, 3-methylbutanal, propanal, butanal,
pentanal, hexanal, heptanal, octanal, nonanal, decanal,
benzaldehyde, 2-propenal, 3-methyl-2-butenal, (E)-2-hexanal,
(E)-2-octenal, (E)-2-nonenal and (E,E)-2,4-decadienal.
19. The method of claim 17 or 18, wherein at least one free
carbonyl compound in the starting distilled alcoholic spirit is
reduced through a conversion to an acetal or hemi-acetal.
20. The method of any one of claims 1-16, wherein at least one free
carbonyl compound is a ketone.
21. The method of claim 20, wherein the ketone is selected from
2-butanone, 2-pentanone, 2-heptanone, 2,3-butendione and
2,3-pentendione.
22. The method of claim 20 or 21, wherein at least one free
carbonyl compound in the starting distilled alcoholic spirit is
reduced through a conversion to a ketal or hemi-ketal.
23. The method of any one of claims 1-22, further comprising
contacting the starting distilled alcoholic spirit with a carbonyl
scavenger agent.
24. The method of any one of claims 1-23, further comprising
contacting the modified distilled alcoholic spirit with a carbonyl
scavenger agent.
25. The method of claim 24, wherein contacting the modified
distilled alcoholic spirit with the carbonyl scavenger agent causes
at least one free carbonyl compound in the modified distilled
alcoholic spirit to be reduced.
26. The method of any one of claims 23-25, wherein the carbonyl
scavenger agent is selected from an alcohol, a sulfite and an
amine- or amide-containing molecule.
27. The method of claim 26, wherein the carbonyl scavenger agent is
an alcohol.
28. The method of claim 27, wherein the carbonyl scavenger agent is
trehalose.
29. The method of claim 26, wherein the carbonyl scavenger is an
amine-containing molecule.
30. The method of claim 26, wherein the carbonyl scavenger is an
amide-containing molecule.
31. The method of claim 26, wherein the carbonyl scavenger is a
sulfite.
32. The method of claim 31, wherein the sulfite is sodium
bisulfile.
33. The method of any one of claims 23-32, wherein the carbonyl
scavenger agent is a food grade additive.
34. The method of any one of claims 23-25, wherein the carbonyl
scavenger agent is bound to a polymer.
35. The method of claim 34, wherein the carbonyl scavenger agent is
a polymer bound sulfonyl hydrazine.
36. The method of claim 34, wherein the carbonyl scavenger is a
polymer bound tosyl hydrazine.
37. The method of any one of claim 1-36, further comprising
contacting the starting or modified distilled alcoholic spirit with
at least one aldehyde, wherein the aldehyde is cinnamic aldehyde or
vanillin.
38. The method of any one of claims 1-37, wherein the at least one
free carbonyl compound in the starting distilled alcoholic spirit
is reduced in about two weeks.
39. The method of any one of claims 1-37, wherein the at least one
free carbonyl compound in the starting distilled alcoholic spirit
is reduced by at least about 20% by weight in about two weeks.
40. The method of any one of claims 1-37, wherein the at least one
free carbonyl compound in the starting distilled alcoholic spirit
is reduced by at least about 20% by weight in about 1 week.
41. The method of any one of claims 1-37, wherein the at least one
free carbonyl compound in the starting distilled alcoholic spirit
is reduced by at least about 20% by weight in about 3 days.
42. The method of any one of claims 1-41, wherein the trigeminal
ethanol related burn, smoothness, taste, aroma and/or flavor
profile of the modified distilled alcoholic spirit is improved over
the starting distilled alcoholic spirit.
43. A modified distilled alcoholic spirit prepared by the methods
of any one of claims 1-42.
44. A modified distilled alcoholic spirit comprising at least one
free carbonyl compound, wherein the at least one free carbonyl
compound is reduced as compared to a corresponding unmodified
distilled alcoholic spirit.
45. A non-aged distilled alcoholic spirit with a pH greater than or
equal to about 7.
46. The non-aged distilled alcoholic spirit of claim 45, wherein
the pH is greater than or equal to about 8.
47. A method of preparing a modified mouthwash comprising providing
a corresponding starting mouthwash with a pH less than about 5.5
and contacting it with a base to provide a modified mouthwash with
a pH greater than about 6.
48. The method of claim 47, wherein the pH of the starting
mouthwash is less than about 5.
49. The method of claim 47, wherein the pH of the starting
mouthwash is less than about 4.
50. The method of any one of claims 47-49, wherein the pH of the
modified mouthwash is greater than about 7.
51. The method of any one of claims 47-49, wherein the pH of the
modified mouthwash is greater than about 8.
52. The method of any one of claims 47-51, wherein the starting
mouthwash has an alcohol by volume content of at least about
5%.
53. The method of any one of claims 47-51, wherein the starting
mouthwash has an alcohol by volume content of at least about
15%.
54. The method of any one of claims 47-53, wherein at least one
free carbonyl compound in the starting mouthwash is reduced by at
least about 20% by weight.
55. The method of any one of claims 47-53, wherein at least one
free carbonyl compound in the starting mouthwash is reduced by at
least about 50% by weight.
56. The method of any one of claims 47-53, wherein at least one
free carbonyl compound in the starting mouthwash is reduced by at
least about 80% by weight.
57. The method of any one of claims 47-56, wherein the at least one
free carbonyl compound is an aldehyde.
58. The method of any one of claims 47-56, wherein the at least one
free carbonyl compound is a ketone.
59. The method of any one of claims 47-58, wherein the base is a
food grade additive.
60. The method of any one of claims 47-59, wherein the base is
sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium
hydroxide, potassium carbonate or potassium bicarbonate.
61. The method of any one of claims 47-60, further comprising
contacting the starting mouthwash with a carbonyl scavenger
agent.
62. The method of any one of claims 47-61, further comprising
contacting the modified mouthwash with a carbonyl scavenger
agent.
63. The method of claim 62, wherein contacting the modified
mouthwash with the carbonyl scavenger agent causes at least one
free carbonyl compound in the modified mouthwash to be reduced.
64. The method of any one of claims 61-63, wherein the carbonyl
scavenger agent is selected from an alcohol, a sulfite and an
amine- or amide-containing molecule.
65. The method of any one of claims 61-64, wherein the carbonyl
scavenger agent is a food grade additive.
66. The method of any one of claims 61-63, wherein the carbonyl
scavenger agent is bound to a polymer.
67. The method of any one of claims 54-66, wherein at least one
free carbonyl compound in the starting mouthwash is reduced by at
least about 20% by weight in about two weeks.
68. The method of any one of claims 54-66, wherein at least one
free carbonyl compound in the starting mouthwash is reduced by at
least about 20% by weight in about 1 day.
69. The method of any one of claims 47-68, wherein the trigeminal
ethanol related burn, smoothness, taste, aroma and/or flavor
profile of the modified mouthwash is improved over the starting
mouthwash.
70. A modified mouthwash prepared by the methods of any one of
claims 47-69.
71. A modified mouthwash comprising at least one free carbonyl
compound, wherein the at least one free carbonyl compound is
reduced as compared to a corresponding unmodified mouthwash.
72. A mouthwash with a pH greater than about 6 and an alcohol by
volume content of at least 5%.
73. The mouthwash of claim 72, wherein the mouthwash has improved
trigeminal ethanol related burn, smoothness, taste, aroma and/or
flavor profile in comparison to a corresponding mouthwash with a pH
less than about 6 and an alcohol by volume content of at least
about 5%.
74. A method of preparing a modified medicament comprising
providing a corresponding starting medicament with a pH less than
about 5 and contacting it with a base to provide a modified
medicament with a pH greater than about 6, wherein the modified
medicament has an alcohol by volume of at least about 5%.
75. The method of claim 74, wherein the pH of the starting
medicament is less than about 4.
76. The method of claim 74, wherein the pH of the starting
medicament is less than about 3.
77. The method of claim 74, wherein the pH of the modified
medicament is greater than about 7.
78. The method of claim 74, wherein the pH of the modified
medicament is greater than about 8.
79. The method of any one of claims 74-78, wherein the starting
medicament has an alcohol by volume content of at least about
10%.
80. The method of any one of claims 74-78, wherein the starting
medicament has an alcohol by volume content of at least about
15%.
81. The method of any one of claims 74-78, wherein the starting
medicament has an alcohol by volume content of at least about
20%.
82. The method of any one of claims 74-81, wherein the starting
medicament comprises at least one of a cough suppressant, an
expectorant, a pain reliever, a fever reducer agent, an analgesic
agent, a vasodilator agent, an antihistamine or an antispasmodic
agent.
83. The method of any one of claims 74-82, wherein at least one
free carbonyl compound in the starting medicament is reduced by at
least about 20% by weight.
84. The method of any one of claims 74-82, wherein at least one
free carbonyl compound in the starting medicament is reduced by at
least about 50% by weight.
85. The method of any one of claims 74-82, wherein at least one
free carbonyl compound in the starting medicament is reduced by at
least about 80% by weight.
86. The method of any one of claims 83-85, wherein the at least one
free carbonyl compound is an aldehyde.
87. The method of any one of claims 83-85, wherein the at least one
free carbonyl compound is a ketone.
88. The method of any one of claims 74-87, wherein the base is
sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium
carbonate, potassium bicarbonate or potassium hydroxide.
89. The method of any one of claims 74-88, wherein the base is a
food grade additive.
90. The method of any one of claims 74-89, further comprising
contacting the starting medicament with a carbonyl scavenger
agent.
91. The method of any one of claims 74-90, further comprising
contacting the modified medicament with a carbonyl scavenger
agent.
92. The method of claim 91, wherein contacting the modified
medicament with the carbonyl scavenger agent causes at least one
free carbonyl compound in the modified medicament to be
reduced.
93. The method of any one of claims 90-92, wherein the carbonyl
scavenger agent is selected from an alcohol, a sulfite and an
amine- or amide-containing molecule.
94. The method of any one of claims 90-93, wherein the carbonyl
scavenger agent is a food grade additive.
95. The method of any one of claims 90-92, wherein the carbonyl
scavenger agent is bound to a polymer.
96. The method of any one of claims 83-95, wherein the at least one
free carbonyl compound in the starting medicament is reduced by at
least about 20% by weight in about two weeks.
97. The method of any one of claims 83-95, wherein the at least one
free carbonyl compound in the starting medicament is reduced by at
least about 20% by weight in about 3 days.
98. The method of any one of claims 74-97, wherein the trigeminal
ethanol related burn, smoothness, taste, aroma and/or flavor
profile of the modified medicament is improved over the starting
medicament.
99. A modified medicament prepared by the methods of any one of
claims 74-98.
100. A modified medicament comprising at least one free carbonyl
compound, wherein the modified medicament has an alcohol by volume
of at least about 5%, and wherein the at least one free carbonyl
compound is reduced as compared to a corresponding unmodified
medicament.
101. The modified medicament of claim 100, wherein the at least one
free carbonyl compound in the modified medicament is reduced by at
least about 20% by weight as compared to the corresponding
unmodified medicament.
102. A medicament with a pH greater than about 5 and an alcohol by
volume content of at least about 5%.
103. The medicament of claim 102, wherein the medicament has
improved trigeminal ethanol related burn, smoothness, taste, aroma
and/or flavor profile in comparison to a corresponding medicament
with a pH less than about 5 and an alcohol by volume content of at
least about 5%.
104. The medicament of any one of claims 100-103, wherein the
medicament comprises at least one of a cough suppressant, an
expectorant, a pain reliever, a fever reducer agent, an analgesic
agent, a vasodilator agent, an antihistamine or an antispasmodic
agent.
105. A method of preparing a modified beer, comprising contacting a
corresponding starting beer with a base under conditions that cause
at least one free carbonyl compound in the starting beer to be
reduced, to provide the modified beer.
106. The method of claim 105, wherein the modified beer has an
alcohol by volume of at least about 1%.
107. The method of any one of claims 105-106, wherein the pH of the
starting beer is about 2.5 to 5.
108. The method of any one of claims 105-107, wherein the pH of the
modified beer is about 3 to about 7.5.
109. The method of any one of claims 105-108, wherein at least one
free carbonyl compound is reduced by at least about 20% by
weight.
110. The method of any one of claims 105-109, further comprising
contacting the starting beer or the modified beer with a carbonyl
scavenger agent.
111. A modified beer prepared by the methods of any one of claims
105-110.
112. The modified beer of claim 111, wherein the modified beer has
an alcohol by volume of at least about 1%.
Description
RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional
Application No. 61/982,228, filed 21 Apr. 2014, the entire content
of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Flavor is a complex sensation. The chemical stimuli of a
flavor response typically consist of numerous compounds. Flavor
compounds are commonly categorized into different modalities such
as taste (gustation; sweet, sour, salty, bitter, umami), aroma
(olfaction) and chemesthetic (chemical irritation of trigeminal
nerves--heat, cooling, pain) sensations. Ethyl alcohol and
alcoholic products as manufactured have a characteristic burn
flavor (chemestetic sensation) that is distinct from aroma or
taste, and which is typically viewed as a negative product
attribute. Currently there is a need for methods able to modify
alcohol containing products resulting in reduction of this burn
flavor. In particular, there is a need for methods to modify
distilled alcoholic spirits that are not typically processed by
purification techniques beyond distillation (e.g., filtration),
such as whiskey, rum, brandy, tequila, gin and other alcoholic
distilled spirits to reduce this trigeminal burn sensation
typically associated with alcohol. Additionally there is a need to
develop processing technologies that can accelerate the aging
process of distilled alcoholic spirits that contribute to favorable
flavor changes, such as improving smoothness perception and
reducing burn flavor. In particular, there is a need for methods
for "accelarated aging" for products such as brandy and whiskey
which require years of aging thus, reducing production cost whilst
maintaining the sensory quality of the final product.
SUMMARY OF THE INVENTION
[0003] Accordingly, the invention provides methods for modifying
alcoholic products to reduce burn flavor. In particular, these
methods modify distilled alcoholic spirits, such as whiskey, rum,
brandy, tequila, soju, gin, baijiu and other alcoholic distilled
spirits, which are typically not processed by purification
techniques, to reduce burn flavor. In addition to reducing alcohol
burn, these methods may also positively impart maturation and
result in a more desirable smoothness perception, cleaner overall
flavor profile and/or increased consumer palatability. In certain
embodiments, these results may be obtained without the addition of
high amounts of sweeteners (sugars, high intensity sweeteners,
etc.).
[0004] Certain embodiments of the invention provide a method of
preparing a modified distilled alcoholic spirit, comprising
contacting a corresponding starting distilled alcoholic spirit with
a base under conditions that cause at least one free carbonyl
compound in the starting distilled alcoholic spirit to be reduced,
to provide the modified distilled alcoholic spirit that has an
alcohol by volume (ABV) of at least about 15%.
[0005] Certain embodiments of the invention provide a method of
preparing a modified distilled alcoholic spirit, comprising
contacting a corresponding starting distilled alcoholic spirit with
a base under conditions that cause the total of free carbonyl
compounds in the starting distilled alcoholic spirit to be reduced,
to provide the modified distilled alcoholic spirit that has an
alcohol by volume (ABV) of at least about 15%.
[0006] Certain embodiments of the invention provide a modified
distilled alcoholic spirit prepared by the methods described
herein.
[0007] Certain embodiments of the invention provide a modified
distilled alcoholic spirit comprising at least one free carbonyl
compound, wherein the at least one free carbonyl compound is
reduced as compared to a corresponding unmodified distilled
alcoholic spirit.
[0008] Certain embodiments of the invention provide a non-aged
distilled alcoholic spirit with a pH greater than or equal to about
7.
[0009] Certain embodiments of the invention provide a method of
preparing a modified mouthwash comprising providing a corresponding
starting mouthwash with a pH less than about 5.5 and contacting it
with a base to provide a modified mouthwash with a pH greater than
about 6.
[0010] Certain embodiments of the invention provide a modified
mouthwash prepared by the methods described herein.
[0011] Certain embodiments of the invention provide a modified
mouthwash comprising at least one free carbonyl compound, wherein
the at least one free carbonyl compound is reduced as compared to a
corresponding unmodified mouthwash.
[0012] Certain embodiments of the invention provide a mouthwash
with a pH greater than about 6 and an alcohol by volume content of
at least 5%.
[0013] Certain embodiments of the invention provide a method of
preparing a modified medicament comprising providing a
corresponding starting medicament with a pH less than about 5 and
contacting it with a base to provide a modified medicament with a
pH greater than about 6, wherein the modified medicament has an
alcohol by volume of at least about 5%.
[0014] Certain embodiments of the invention provide a modified
medicament prepared by the methods described herein.
[0015] Certain embodiments of the invention provide a modified
medicament comprising at least one free carbonyl compound, wherein
the modified medicament has an alcohol by volume of at least about
5%; and wherein the at least one free carbonyl compound is reduced
as compared to a corresponding unmodified medicament.
[0016] Certain embodiments of the invention provide a medicament
with a pH greater than about 5 and an alcohol by volume content of
at least about 5%.
[0017] Certain embodiments of the invention provide a method of
preparing a modified beer, comprising contacting a corresponding
starting beer with a base under conditions that cause at least one
free carbonyl compound in the starting beer to be reduced, to
provide the modified beer.
[0018] Certain embodiments of the invention provide a modified beer
prepared by the methods described herein.
BRIEF DESCRIPTION OF THE FIGURES
[0019] FIG. 1. Experimental protocol for carbonyl species
scavenging and sensory evaluation of water/ethanol samples.
Acetaldehyde was added as internal standard prior to trapping at
levels of 5 mM.
[0020] FIG. 2. Aldehyde and ketone scavenging polymer agents and
trapping reaction mechanism.
[0021] FIG. 3. Experimental protocol for carbonyl species
scavenging and sensory evaluation of water/ethanol samples.
[0022] FIG. 4. Levels of carbonyl species present in water/ethanol
(60/40) solutions with modified pH at 3.0, (left bar), 6.3 (middle
bar) and 8.0 (right bar). Results are presented in mg/L and were
obtained by DHS GC/MS
[0023] FIG. 5. Levels of carbonyl species present in water/ethanol
(60/40) solution (pH 6.3, left bar) and water/ethanol (60/40)
solution treated with sulfonyl hydrazine (pH 6.3, right bar).
Results are presented in mg/L and were obtained by DHS GC/MS.
[0024] FIG. 6. Levels of carbonyl species present in water with
adjusted pH 8.0 (left bar) and water with adjusted pH 3.0 (right
bar) after addition of 10 ppm of butanal, hexanal, heptanal,
octanal, nonanal, decanal and benzaldehyde. Results are presented
in relative percent and were obtained by DHS GC/MS.
[0025] FIG. 7. Selected NMR spectra areas indicating differences
between water/ethanol pH 8.0+500 ppm aldehyde solution (top line)
and water/ethanol pH 3.0+500 ppm aldehyde solution (bottom line).
Aldehydes added: butanal, hexanal, heptanal, octanal, nonanal,
decanal and benzaldehyde.
[0026] FIG. 8. Effect of trehalose on carbonyl species present in
Karkov vodka. Karkov pH 3.0, (left bar), Karkov pH 3.0 trehalose
(middle bar), Karkov pH 8.0 trehalose (right bar). Results are
presented in area percent reduction and were obtained by DHS
GC/MS-SIM. Highest peak area was adjusted to 100%.
[0027] FIG. 9. Smoothness and burning sensation rating of ZYR and
Karkov vodkas at different pH values. Smoothness/burning sensation
was rated as compared to a standard scale constructed of different
levels of glycerin in 40% ethanol solution.
[0028] FIG. 10. Experimental protocol for carbonyl species
scavenging and sensory evaluation of vodka samples.
[0029] FIG. 11. Overlaid dynamic headspace chromatograms of Karkov
and Zyr with internal standard from top to bottom.
[0030] FIG. 12. Overlaid NMR spectra of Zyr and Karkov vodkas.
Selected areas indicate area of differentiation between the
samples.
[0031] FIG. 13. Selected NMR spectra areas indicating differences
between Zyr and Karkov. (a) 5.5-5.3 ppm region, (b) 4.3-3.6 ppm and
(c) 3.2-2.5 ppm.
[0032] FIG. 14. Experimental protocol for carbonyl species
quantification. Acetaldehyde was added as internal standard prior
to trapping at levels of 5 mM.
[0033] FIG. 15. Experimental protocol to test the effect of sample
pH on volatility. *butanal, hexanal, heptanal, octanal, nonanal,
decanal and benzaldehyde.
[0034] FIG. 16. Levels of carbonyl species present in Karkov vodka
(pH 3.0, left bar) and modified Karkov vodka (pH 8.0, right bar).
Results are presented in mg/L and were obtained by DHS GC/MS.
[0035] FIG. 17. Levels of carbonyl species present in water with
adjusted pH 8.0 (left bar) and water with adjusted pH 3.0 (right
bar) after addition of 10 ppm of butanal, hexanal, heptanal,
octanal, nonanal, decanal and benzaldehyde. Results are presented
in relative percent and were obtained by DHS GC/MS.
[0036] FIG. 18. Selected NMR spectra areas indicating differences
between Karkov pH 8.0+500 ppm aldehyde solution (top line) and
Karkov pH 3.0+500 ppm aldehyde solution (bottom line). Aldehydes
added: butanal, hexanal, heptanal, octanal, nonanal, decanal and
benzaldehyde.
[0037] FIG. 19. Levels of carbonyl species present in the
following, listed from left to right for each group: Karkov vodka
(pH 3.0) and Karkov vodka (pH 3.0, treated with sulfonyl
hydrazine), modified Karkov vodka (pH 8.0) and modified Karkov
vodka (pH 8.0, treated with sulfonyl hydrazine). Results are
presented in mg/L and were obtained by DHS GC/MS.
[0038] FIG. 20. Effect of sodium hydroxide and sodium bicarbonate
on carbonyl species present in Karkov vodka. For each group, the
following were tested and are shown from left to right: Karkov pH
3.0, Karkov pH 8.0 w/sodium hydroxide (SH), and Karkov pH 8.0
w/sodium carbonate (SC). Results are presented in area percent
reduction and were obtained by DHS GC/MS-SIM. Highest peak area was
adjusted to 100%.
[0039] FIG. 21. Effect of trehalose on carbonyl species present in
Karkov vodka. For each group, the following were tested and are
shown from left to right: Karkov pH 3.0, Karkov pH 3.0 trehalose,
Karkov pH 8.0 trehalose. Results are presented in area percent
reduction and were obtained by DHS GC/MS-SIM. Highest peak area was
adjusted to 100%.
DETAILED DESCRIPTION
[0040] Certain embodiments of the invention provide methods to
reduce the burn flavor attributes of ethyl alcohol and
alcohol-containing products, such as oral care and hygiene products
(e.g., mouthwash), medicaments (e.g., cough medicine, expectorant
syrups), and spirits (e.g., whiskey, rum and brandy). Ethyl alcohol
and alcoholic products as manufactured have a characteristic burn
flavor (chemestetic sensation) that is typically viewed as a
negative product attribute. As described herein, the burn of ethyl
alcohol is not mainly due to ethyl alcohol itself as previously
thought but is largely influenced by the chemical composition (i.e.
carbonyl compounds) of the product. By altering the chemical
composition of ethyl alcohol, specifically the free carbonyl
compounds (i.e. aldehydes and ketones), the perceived burn
intensity of ethyl alcohol and alcoholic containing products can be
modified. The chemical composition of carbonyl compounds in ethyl
alcohol can be altered by 1) adjusting the pH of the product; 2)
the addition of compounds or scavenger agents that react with
aldehydes/ketones and thereby decrease the free concentration of
aldehydes/ketones (i.e. acetal reactions); 3)
extraction/isolation/filtration techniques that remove
aldehydes/ketones; 4) or a combination of these techniques.
[0041] As described herein, an equilibrium reaction exists between
carbonyl compounds and alcohols (reactants) to hemiacetals and
acetals (products) that is pH dependent in ethyl alcohol and
alcoholic products, such as distilled spirits. Both saturated and
unsaturated aldehydes (and ketones) are reactive and will react
with alcohol containing compounds (i.e. ethyl alcohol) to form
hemi-acetals/acetals (or hemi-ketals/ketals) and the equilibrium of
this reaction is pH dependent. At a lower pH values, the
equilibrium favors the free "carbonyls" (aldehydes and ketones) and
consequently lower levels of hemi-acetals/acetals (or
hemi-ketals/ketals) products. At higher pH values, the equilibrium
favors hemiacetals/acetals formation and consequently lower levels
of free "carbonyls" (aldehydes and ketones). If the pH of the
alcoholic product is increased (range from 2-12), the concentration
of free carbonyls will decrease and the ethyl alcohol or
alcohol-containing product will have lower burn intensity (smoother
flavor). This equilibrium can additionally be beneficial as the
increased acetal species can positively impart smoothness and
maturation, as they are associated with pleasant aroma attributes
contrary to their pungent aldehyde counterparts. This improved
alcohol flavor (less burn) has been demonstrated by increasing the
pH with economical food grade ingredients, such as sodium
hydroxide, sodium carbonate and sodium bicarbonate (see, Examples).
This has been shown using analytical experiments that show lower
levels of aldehydes exist at a higher product pH and through
sensory analysis (human analysis), which confirmed these samples
(e.g., vodka, brandy, ethyl alcohol, mouthwash) had a perceived
lower alcohol burn intensity. Additionally, as described herein,
the addition of select alcoholic compounds, such as trehalose, also
causes a reduction in alcohol burn (e.g., by reducing
carbonyls).
[0042] In certain embodiments of the invention, the methods target
a reduction of alcohol burn and result in a more desirable
smoothness perception, cleaner overall flavor profile and/or
increased consumer palatability. In certain embodiments, these
results may be obtained without the addition of high amounts of
sweeteners (e.g., sugars, high intensity sweeteners, etc.).
Distilled Alcoholic Spirits
[0043] Certain embodiments of the invention provide a method of
preparing a modified distilled alcoholic spirit, comprising
contacting a corresponding starting distilled alcoholic spirit with
a base under conditions that cause at least one free carbonyl
compound in the starting distilled alcoholic spirit to be reduced,
to provide the modified distilled alcoholic spirit that has an
alcohol by volume (ABV) of at least about 15%. In certain
embodiments, the distilled alcoholic spirit has an ABV of at least
about 20%, at least about 30%, at least about 40%, at least about
45% or more.
[0044] Certain embodiments of the invention provide a method of
preparing a modified distilled alcoholic spirit, comprising
contacting a corresponding starting distilled alcoholic spirit with
a base under conditions that cause the total of free carbonyl
compounds in the starting distilled alcoholic spirit to be reduced,
to provide the modified distilled alcoholic spirit that has an
alcohol by volume (ABV) of at least about 15%. In certain
embodiments, the distilled alcoholic spirit has an ABV of at least
about 20%, 30%, 40%, 45% or more.
[0045] In certain embodiments, a distilled alcoholic spirit is any
beverage comprising alcohol, which is produced by distillation of a
mixture produced from alcoholic fermentation, such as wine. For
example, in certain embodiments, the distilled alcoholic spirit may
be whiskey, rum, brandy, tequila, soju, gin or baiju. In certain
embodiments, the distilled alcoholic spirit is not vodka.
[0046] Typically, a whiskey is an alcoholic distillate from a
fermented mash of grain produced at less than 190.degree. proof
(i.e., 95% ABV) in such manner that the distillate possesses the
taste, aroma, and characteristics generally attributed to whisky,
stored in oak containers (except that corn whisky need not be so
stored), and bottled at not less than 80.degree. proof (i.e., 40%
ABV), and also includes mixtures of such distillates for which no
specific standards of identity are prescribed (see, e.g., 27 C.F.R.
.sctn.5.22, which provides standards of identity for certain
classes and types of distilled spirits). In certain embodiments,
the whiskey may be a bourbon whiskey, a rye whiskey, a wheat
whiskey, a malt whiskey, a rye malt whiskey, a corn whiskey,
straight bourbon whiskey, a straight rye whiskey, a straight wheat
whiskey, a straight malt whiskey, a straight rye malt whiskey, a
straight corn whiskey, a whisky distilled from bourbon (rye, wheat,
malt, or rye malt) mash, a light whisky, a blended whisky, a blend
of straight whiskies, a spirit whisky, a scotch whisky, an Irish
whisky, or a Canadian whisky.
[0047] Typically, a rum is an alcoholic distillate from the
fermented juice of sugar cane, sugar cane syrup, sugar cane
molasses, or other sugar cane by-products, produced at less than
190.degree. proof (i.e., 95% ABV) in such manner that the
distillate possesses the taste, aroma, and characteristics
generally attributed to rum, and bottled at not less than
80.degree. proof (i.e., 40% ABV); and also includes mixtures solely
of such distillates (see, e.g., 27 C.F.R. .sctn.5.22).
[0048] Typically, a brandy is an alcoholic distillate from the
fermented juice, mash, or wine of fruit, or from the residue
thereof, produced at less than 190.degree. proof (i.e., 95% ABV) in
such manner that the distillate possesses the taste, aroma, and
characteristics generally attributed to the product, and bottled at
not less than 80.degree. proof (i.e., 40% ABV) (see, 27 C.F.R.
.sctn.5.22). In certain embodiments, the brandy may be a fruit
brandy, cognac or cognac (grape) brandy, dried fruit brandy, lees
brandy, pomace brandy or marc brandy, residue brandy, neutral
brandy, eau de vie (i.e., a clear fruit brandy, such as, e.g.,
snap) or a substandard brandy.
[0049] Typically, tequila is an alcoholic distillate from a
fermented mash derived, e.g., principally from the Agave Tequilana
Weber ("blue" variety), with or without additional fermentable
substances, distilled in such a manner that the distillate
possesses the taste, aroma, and characteristics generally
attributed to Tequila and bottled at not less than 80.degree. proof
(i.e., 40% ABV), and also includes mixtures solely of such
distillates. Generally, tequila is a distinctive product of Mexico,
manufactured in Mexico in compliance with the laws of Mexico
regulating the manufacture of Tequila for consumption in that
country (see, e.g., 27 C.F.R. .sctn.5.22).
[0050] Typically, soju refers to a distilled beverage that is
native to Korea. It is traditionally made from rice, wheat, barley,
as well as other starches, such as potatoes, sweet potatoes, or
tapioca depending on the desired sweetness of the end product. Soju
is typically a clear and colorless distilled beverage and its
alcohol content may vary from about 16.7%, to about 45% alcohol by
volume (ABV) with 20% ABV being most popular. Soju may be produced
by two different ways to yield distilled and diluted soju. The
classic way of distilling soju uses a single distillation method
yielding a higher alcohol content spirit and the modern way of
diluted soju that uses the chain distillation method to yield a
spirit with lower ABV (.about.20%). Addition of sugar during the
distillation step(s) is also common practice affording the beverage
sweet taste. The addition of sugar, the variable distillation
methods employed and final alcohol content differentiates soju from
vodka, which generally has a minimum ABV of 37.5%.
[0051] Typically, gin is a product obtained by original
distillation from mash, or by redistillation of distilled spirits,
or by mixing neutral spirits, with or over juniper berries and
other aromatics, or with or over extracts derived from infusions,
percolations, or maceration of such materials, and includes
mixtures of gin and neutral spirits. It typically derives its main
characteristic flavor from juniper berries and is bottled at not
less than 80.degree. proof (i.e., 40% ABV). Gin produced
exclusively by original distillation or by redistillation may be
further designated as "distilled". In certain embodiments, the gin
may be "Dry gin" (London dry gin), "Geneva gin" (Hollands gin), or
"Old Tom gin" (Tom gin).
[0052] Typically, baiju refers to a distilled spirit produced
predominantly in China. Generally it is produced through
fermentation and distillation of sorghum or rice, but sometimes
other grains, legumes, vegetables or fruit is used to produce a
spirit with an alcohol by volume (ABV) content of 40-60%. The jiuqu
starter culture used in the production of baijiu mash, or more
commonly known as Qu, is usually made of pulverized wheat grains
and can contain Chinese medicinal herbs, mixed with water and
formed into bricks or balls that are stored in a warm, damp
environment for about a month. The Qu is then filled with yeasts,
fungi and other types of microorganisms to merge saccharification
and fermentation steps for production of alcohol. Fermentation of
Baijiu takes places in subterranean mud pits, ceramic jars or in
jars buried underground and can be single or multiple cycle
process. When fermentation is complete distillation takes place to
yield baijiu. After distillation, baijiu is commonly aged in
earthenware urns in underground cellars, caves or dark rooms for at
least one to two years. Once the baijiu is aged, the desired amount
is bottled or diluted to taste and to achieve an ABV of 40-60%
(most commonly 48-56%).
[0053] In certain embodiments, the distilled alcoholic spirit is
whiskey. In certain embodiments, the distilled alcoholic spirit is
rum. In certain embodiments, the distilled alcoholic spirit is
brandy (e.g., eau de vie). In certain embodiments, the distilled
alcoholic spirit is tequila. In certain embodiments, the distilled
alcoholic spirit is gin. In certain embodiments, the distilled
alcoholic spirit is baiju. In certain embodiments, the distilled
alcoholic spirit is soju.
[0054] In certain embodiments, the pH of the starting distilled
alcoholic spirit is about 2.5 to about 5.5 (e.g., about 2.5, 2.6,
2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9,
4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2,
5.3, 5.4 or 5.5).
[0055] In certain embodiments, the pH of the starting distilled
alcoholic spirit is about 2.5 to about 4.5 (e.g., about 2.5, 2.6,
2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9,
4.0, 4.1, 4.2, 4.3, 4.4 or 4.5).
[0056] In certain embodiments, the pH of the starting distilled
alcoholic spirit is about 3 to about 5.5 (e.g., about 3.0, 3.1,
3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 4.0, 4.1, 4.2, 4.3, 4.4,
4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4 or 5.5).
[0057] In certain embodiments, the pH of the starting distilled
alcoholic spirit is about 3 to about 4.4 (e.g., about 3.0, 3.1,
3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 4.0, 4.1, 4.2 or 4.3).
[0058] In certain embodiments, the pH of the modified distilled
alcoholic spirit is about 5 to about 12 (e.g., about 5, 5.5, 6,
6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 or 12).
[0059] In certain embodiments, the pH of the modified distilled
alcoholic spirit is about 5.5 to about 12 (e.g., about 5.5, 6, 6.5,
7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 or 12).
[0060] In certain embodiments, the pH of the modified distilled
alcoholic spirit is about 6 to about 8.5 (e.g., about 6, 6.1, 6.2,
6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5,
7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5).
[0061] As used herein, a base is a substance (e.g., in a solid or
liquid form) that will increase the pH of the starting distilled
alcoholic spirit. In certain embodiments, the base is a solid. In
certain embodiments, the base is a liquid. In certain embodiments,
the base is a food grade additive. In certain embodiments, the base
is sodium bicarbonate, sodium carbonate, sodium hydroxide,
potassium hydroxide, potassium carbonate or potassium bicarbonate.
In certain embodiments, the base is sodium carbonate.
[0062] In certain embodiments, the at least one free carbonyl
compound is reduced by at least about 10, 20, 25, 30, 35, 40, 45,
50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by
weight. In certain embodiments, the at least one free carbonyl
compound is reduced by at least about 10% by weight. In certain
embodiments, the at least one free carbonyl compound is reduced by
at least about 20% by weight.
[0063] In certain embodiments, more than one free carbonyl compound
is reduced.
[0064] In certain embodiments, the total of the free carbonyl
compounds is reduced by at least about 10% by weight. Accordingly,
as used herein, the total weight of the free carbonyl compounds in
the starting distilled alcoholic spirit must be reduced by about
10% (e.g., certain free carbonyl species may be reduced while other
species may be unchanged or increased). In certain embodiments, the
total of the free carbonyl compounds is reduced by at least about
20% by weight. Accordingly, as used herein, the total weight of the
free carbonyl compounds in the starting distilled alcoholic spirit
must be reduced by about 20% (e.g., certain free carbonyl species
may be reduced while other species may be unchanged or increased).
In certain embodiments, the total of the free carbonyl compounds is
reduced by at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by weight.
[0065] Quantitative changes in levels of free carbonyl compounds
(e.g., aldehydes or ketones) and other relevant chemical species
(e.g., acetals, hemi-acetals, ketals or hemi-ketals) can be
determined by one skilled in the art using common analytical
methods for volatile analysis known in the art, such as Gas
Chromatography-Mass Spectroscopy (GC-MS) coupled with various
sample preparation methods, such as Headspace, solvent extraction
or distillation methods. (DG. Peterson, G A Reineccius and MC Qian
(2010). Gas Chromatography. In S. S. Nielsen (Ed.), Food Analysis
(4.sup.th Ed.) (p.p. 513-537). New York, N.Y. Springer
Science+Business Media LLC.). Additionally, techniques such as
Nuclear Magnetic Resonance spectroscopy (NMR) can be used to
qualitatively confirm changes of free carbonyl compounds. Examples
of methods for measuring both qualitative and quantitative changes
are presented below in Examples 1, 2 and 3.
[0066] As used herein a free carbonyl compound includes aldehydes
and ketones comprising a C(.dbd.O) functional group.
[0067] In certain embodiments, at least one free carbonyl compound
is an aldehyde. One skilled in the art would understand that an
aldehyde includes compounds of formula: R.sub.xCHO. In certain
embodiments, at least one aldehyde is selected from acetaldehyde,
2-methylbutanal, 3-methylbutanal, propanal, butanal, pentanal,
hexanal, heptanal, octanal, nonanal, decanal and benzaldehyde, as
well as, unsaturated aldehydes such as 2-propenal,
3-methyl-2-butenal, (E)-2-hexanal, (E)-2-octenal, (E)-2-nonenal and
(E,E)-2,4-decadienal.
[0068] In certain embodiments, the at least one free carbonyl
compound is a ketone. One skilled in the art would understand that
a ketone includes compounds of formula: R.sub.xC(.dbd.O)R.sub.x. In
certain embodiments, the at least one ketone is selected from
2-butanone, 2-pentanone, 2-heptanone, 2,3-butendione and
2,3-pentendione.
[0069] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced
through a conversion to an acetal. One skilled in the art would
understand that an acetal includes compounds of formula:
R.sub.x--C(OR.sub.x).sub.2H. In certain embodiments, the at least
one acetal is selected from acetaldehyde diethyl acetal, 2-methyl
butanal diethyl acetal, 2-methylpropanal diethyl acetal,
1,1,3,-triethoxypropane, acetaldehyde di-3-methylbutyl acetal,
ethyl-3-methylbutyl acetal and acetaldehyde 2methylpropyl
3-methylbutyl acetal.
[0070] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced
through a conversion to a hemi-acetal. One skilled in the art would
understand that a hemi-acetal includes compounds of formula:
R.sub.x--C(OH)(OR.sub.x)H.
[0071] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced
through a conversion to a ketal. One skilled in the art would
understand that a ketal includes compounds of formula:
R.sub.x--C(OR.sub.x).sub.2--R.sub.x.
[0072] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced
through a conversion to a hemi-ketal. One skilled in the art would
understand that a hemi-ketal includes compounds of formula:
R.sub.x--C(OR.sub.x)(OH)--R.sub.x.
[0073] Throughout the application (e.g., in the formulas above
describing aldehydes, ketones, acetals, hemi-acetals, ketals and
hemi-ketals), the variable R.sub.x is used to refer to a generic
organic group. In one embodiment, the generic organic group has a
molecular weight less than about 300 daltons, 200 daltons or 100
daltons. In certain embodiments, the generic organic group
comprises between about 1-15 carbon atoms, between about 1-10
carbon atoms or between about 1-5 carbon atoms.
[0074] Certain embodiments of the invention further comprise
contacting the starting distilled alcoholic spirit with a carbonyl
scavenger agent.
[0075] In certain embodiments, the starting distilled alcoholic
spirit is contacted with the base and the carbonyl scavenger agent
simultaneously. In certain embodiments, the starting distilled
alcoholic spirit is contacted with the base and the carbonyl
scavenger agent sequentially. In certain embodiments, the starting
distilled alcoholic spirit is contacted with the base first and
with the carbonyl scavenger agent second. In certain embodiments,
the starting distilled alcoholic spirit is contacted with the
carbonyl scavenger agent first and base second.
[0076] Certain embodiments of the invention further comprise
contacting the modified distilled alcoholic spirit with a carbonyl
scavenger agent. In certain embodiments, contacting the modified
distilled alcoholic spirit with the carbonyl scavenger agent causes
at least one free carbonyl compound in the modified distilled
alcoholic spirit to be reduced.
[0077] As used herein a carbonyl scavenger agent is a molecular
entity capable of reacting with carbonyls to reduce their free
form. In certain embodiments, the carbonyl scavenger agent is
selected from an alcohol, a sulfite and an amine- or
amide-containing molecule.
[0078] In certain embodiments, the carbonyl scavenger agent is an
alcohol. As used herein an alcohol is an organic compound in which
the hydroxyl functional group (--OH) is bound to a saturated carbon
atom. For example, in certain embodiments, the alcohol is a polyol
(i.e., alcohols containing multiple hydroxyl groups). In certain
embodiments, the alcohol is trehalose.
[0079] In certain embodiments the carbonyl scavenger agent is a
sulfite. As used herein a sulfite is a compound that contains the
sulfite ion SO.sub.3.sup.2-. For example, in certain embodiments,
the sulfite is sodium bisulfite.
[0080] In certain embodiments, the carbonyl scavenger agent is an
amine-containing molecule. As used herein, an amine-containing
molecule is an organic compound with a functional group that
contains a basic nitrogen atom with a lone electron pair. Amines
are derivatives of ammonia, wherein one or more hydrogens have been
replaced by an alkyl or aryl group and they can be classified as
primary (R--NH.sub.2), secondary (R, R'--NH), tertiary (R, R',
R''--N) and cyclic amines (R, R', R''--N, wherein R and R' taken
with N forms a ring). As used herein, the term alkyl included both
straight and branched hydrocarbon groups (e.g., a C.sub.1-C.sub.10
alkyl). It is understood that the alkyls can optionally be
substituted. As used herein the term aryl includes a phenyl group
(e.g., radical) and an ortho-fused bicyclic carbocyclic group
(e.g., radical) having about nine to ten ring atoms in which at
least one ring is aromatic.
[0081] It is understood that the aryls can optionally be
substituted. For example, in certain embodiments, the
amine-containing molecule is an anthranilite (e.g., methyl
anthranilite, ethyl anthranilite, cinnamyl anthranilite and
isobutyl anthranilite). In certain embodiments, the
amine-containing molecule is monosodium glutamate.
[0082] In certain embodiments, the carbonyl scavenger agent is an
amide-containing molecule. As used herein, an amide-containing
molecule is a small organic molecule that includes a --C(.dbd.O)N
moiety. In one embodiment, the amide comprises 1-20 carbon atoms.
In one embodiment, the amide comprises 1-10 carbon atoms. In
certain embodiments, the amide may be cyclic or linear. For
example, in certain embodiments, the amide is selected from
lactamide, acetamide, 2-hydroxyethyl lactamide, 2-hydroxyethyl
propionamide, N,N'-bis(2-hydroxyethyl)oxamide and butyramide. In
certain embodiments, the amide is butyramide.
[0083] In certain embodiments, the carbonyl scavenger agent is a
food grade additive (e.g., has GRAS status from the FDA).
[0084] In certain embodiments, the carbonyl scavenger agent is
bound to a polymer (e.g., silica). In certain embodiments, the
polymer bound scavenger agent is removed by, e.g., filtration. In
certain embodiments, polymer bound scavenger reaction by-products
(e.g, a scavenger agent bound to a carbonyl) are removed by, e.g.,
filtration.
[0085] In certain embodiments, the carbonyl scavenger agent is a
polymer bound sulfonyl hydrazine.
[0086] In certain embodiments, the carbonyl scavenger agent is a
polymer bound tosyl hydrazine.
[0087] In certain embodiments, the methods further comprise
contacting the starting or modified distilled alcoholic spirit with
at least one aldehyde (e.g., an aldehyde known to convert into
acetal species with pleasant sensory attributes, such as positive
flavor attributes). In certain embodiments, contacting the starting
distilled alcoholic spirit with the at least one aldehyde results
in a modified distilled alcoholic spirit with improved maturation
qualities (e.g., smoothness). Such aldehydes include but are not
limited to cinnamic aldehyde and vanillin, which may be converted
into cinnamic aldehyde dimethyl acetal and vanillin propylene
glycol acetal, respectively.
[0088] In certain embodiments, the methods further comprise
contacting the starting or modified distilled alcoholic spirit with
at least one ketone (e.g., a ketone known to convert into ketal
species with pleasant sensory attributes, such as positive flavor
attributes). In certain embodiments, contacting the starting
distilled alcoholic spirit with the at least one ketone results in
a modified distilled alcoholic spirit with improved maturation
qualities (e.g., smoothness).
[0089] Certain embodiments of the invention further comprise
contacting the modified distilled alcoholic spirit with a base
(i.e., a second base, which may be the same or different from the
base that is contacted with the starting distilled alcoholic
spirit). In certain embodiments, contacting the modified distilled
alcoholic spirit with the base causes at least one free carbonyl
compound in the modified distilled alcoholic spirit to be reduced
(e.g., by 10% or 20% by weight). In certain embodiments, the
modified distilled alcoholic spirit is contacted with a base at
least about 12 hours, 1 day, 2 days, 3 days, 4 days, 5 days, 6
days, 1 week, 2 weeks, 3 weeks or more after the starting distilled
alcoholic spirit is contacted with a base. In certain embodiments,
the modified distilled alcoholic spirit is contacted with a base
for at least about 12 hours, 1 day, 2 days, 3 days, 4 days, 5 days,
6 days, 1 week, 2 weeks, 3 weeks or more (i.e., until the desired
chemical shift has been observed, such as, e.g., at least one free
carbonyl compound in the modified distilled alcoholic spirit is
reduced (e.g., by about 10%)).
[0090] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced in,
e.g., two weeks (i.e., two weeks from when the starting distilled
alcoholic spirit is contacted by the base). In certain embodiments,
the at least one free carbonyl compound in the starting distilled
alcoholic spirit is reduced in, e.g., about one week, 3 days, 1 day
or 12 hours.
[0091] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced by
at least about 10% by weight in, e.g., two weeks (i.e., two weeks
from when the starting distilled alcoholic spirit is contacted by
the base). In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced by
at least about 10% by weight in, e.g., about 1 week, 3 days, 1 day
or 12 hours.
[0092] In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced by
at least about 20% by weight in, e.g., two weeks (i.e., two weeks
from when the starting distilled alcoholic spirit is contacted by
the base). In certain embodiments, the at least one free carbonyl
compound in the starting distilled alcoholic spirit is reduced by
at least about 20% by weight in, e.g., about 1 week, 3 days, 1 day
or 12 hours.
[0093] In certain embodiments, the total of the free carbonyl
compounds in the starting distilled alcoholic spirit is reduced in,
e.g., two weeks (i.e., two weeks from when the starting distilled
alcoholic spirit is contacted by the base). In certain embodiments,
the total of the free carbonyl compounds in the starting distilled
alcoholic spirit is reduced in, e.g., about one week, 3 days, 1 day
or 12 hours.
[0094] In certain embodiments, the total of the free carbonyl
compounds in the starting distilled alcoholic spirit is reduced by
at least about 10% by weight in, e.g., about two weeks (i.e., two
weeks from when the starting distilled alcoholic spirit is
contacted by the base). In certain embodiments, the total of the
free carbonyl compounds in the starting distilled alcoholic spirit
is reduced by at least about 10% by weight in, e.g., about 1 week,
3 days, 1 day or 12 hours.
[0095] In certain embodiments, the total of the free carbonyl
compounds in the starting distilled alcoholic spirit is reduced by
at least about 20% by weight in, e.g., about two weeks (i.e., two
weeks from when the starting distilled alcoholic spirit is
contacted by the base). In certain embodiments, the total of the
free carbonyl compounds in the starting distilled alcoholic spirit
is reduced by at least about 20% by weight in, e.g., about 1 week,
3 days, 1 day or 12 hours.
[0096] In certain embodiments, the trigeminal ethanol related burn,
smoothness, taste, aroma and/or flavor profile of the modified
distilled alcoholic spirit is improved over the starting distilled
alcoholic spirit. In certain embodiments, the improvement is
determined by a subject sampling the modified and starting
alcoholic distilled spirits and rating them using sensory
techniques such as the degree of difference test or descriptive
analysis (e.g., see Examples below).
[0097] Certain embodiments of the invention provide a modified
distilled alcoholic spirit prepared by the methods described
herein.
[0098] Certain embodiments of the invention provide a distilled
alcoholic spirit comprising less than 0.1% by weight free carbonyl
compounds. In certain embodiments, the distilled alcoholic spirit
comprises less than, e.g., about 0.09, 0.08, 0.07, 0.06, 0.05,
0.04, 0.03, 0.02, 0.01, 0.009, 0.008, 0.007, 0.006, 0.005, 0.004,
0.003, 0.002, 0.001, 0.0009, 0.0008, 0.0007, 0.0006, 0.0005,
0.0004, 0.0003, 0.0002 or 0.0001% by weight free carbonyl
compounds. It is to be understood that the percent by weight of
free carbonyl compounds refers to the total weight of the free
carbonyl compounds in the modified distilled alcoholic spirit.
[0099] For certain distilled alcoholic spirits, such as whiskey,
rum and brandy, aging modifies the flavor profile. As used herein,
aging refers to the period during which, after distillation and
before bottling, a distilled alcoholic spirit has been stored in,
e.g., oak containers. In certain embodiments, the methods of
modifying a distilled alcoholic spirit as described herein may
provide a maturation flavor, as the aging chemistry is accelerated
(e.g., without purification processing). Accordingly, in certain
embodiments, the distilled alcoholic spirit is a non-aged distilled
alcoholic spirit.
[0100] Certain embodiments of the invention provide a modified
distilled alcoholic spirit comprising at least one free carbonyl
compound, wherein the at least one free carbonyl compound is
reduced as compared to a corresponding unmodified distilled
alcoholic spirit. A modified distilled alcoholic spirit is, e.g., a
modified distilled alcoholic spirit prepared according to a method
described herein. An unmodified distilled alcoholic spirit is,
e.g., an unmodified distilled alcoholic spirit that has not been
prepared according to a method described herein. In certain
embodiments, the modified distilled alcoholic spirit is a non-aged
modified distilled alcoholic spirit.
[0101] Certain embodiments of the invention provide a modified
distilled alcoholic spirit comprising free carbonyl compounds,
wherein the total of the free carbonyl compounds are reduced as
compared to the total of free carbonyl compounds in a corresponding
unmodified distilled alcoholic spirit. A modified distilled
alcoholic spirit is, e.g., a modified distilled alcoholic spirit
prepared according to a method described herein. An unmodified
distilled alcoholic spirit is, e.g., an unmodified distilled
alcoholic spirit that has not been prepared according to a method
described herein. In certain embodiments, the modified distilled
alcoholic spirit is a non-aged modified distilled alcoholic
spirit.
[0102] In certain embodiments, the at least one free carbonyl
compound is reduced by at least about 10, 20, 25, 30, 35, 40, 45,
50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by
weight as compared to a corresponding unmodified distilled
alcoholic spirit. In certain embodiments, the at least one free
carbonyl compound is reduced by at least about 10% by weight as
compared to a corresponding unmodified distilled alcoholic spirit.
In certain embodiments, the at least one free carbonyl compound is
reduced by at least about 20% by weight as compared to a
corresponding unmodified distilled alcoholic spirit.
[0103] In certain embodiments, more than one free carbonyl compound
is reduced.
[0104] In certain embodiments, the total of the free carbonyl
compounds is reduced by at least about 10% by weight as compared to
the total of free carbonyl compounds in a corresponding unmodified
distilled alcoholic spirit. Accordingly, as used herein, the total
weight of the free carbonyl compounds in the modified distilled
alcoholic spirit must be reduced by 10% (e.g., certain free
carbonyl species may be reduced while other species may be
unchanged or increased). In certain embodiments, the total of the
free carbonyl compounds is reduced by at least about 20% by weight
as compared to the total of free carbonyl compounds in a
corresponding unmodified distilled alcoholic spirit. Accordingly,
as used herein, the total weight of the free carbonyl compounds in
the modified distilled alcoholic spirit must be reduced by 20%
(e.g., certain free carbonyl species may be reduced while other
species may be unchanged or increased). In certain embodiments, the
total of the free carbonyl compounds is reduced by at least about
10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90,
95, 96, 97, 98, or 99% by weight as compared to the total of free
carbonyl compounds in a corresponding unmodified distilled
alcoholic spirit.
[0105] In certain embodiments, the modified distilled alcoholic
spirit has an ABV of at least about 15% (e.g., at least 20%, 30%,
40%, 45% or more) and the corresponding unmodified distilled
alcoholic spirit has an ABV of at least about 15% (e.g., at least
about 20%, 30%, 40%, 45% or more).
[0106] In certain embodiments, the modified distilled alcoholic
spirit is whiskey. In certain embodiments, the modified distilled
alcoholic spirit is rum. In certain embodiments, the modified
distilled alcoholic spirit is brandy.
[0107] Certain embodiments of the invention provide a non-aged
distilled alcoholic spirit with a pH greater than or equal to about
5, greater than or equal to about 6, greater than equal to about 7,
greater than equal to about 8 or greater than equal to about 9.
[0108] In certain embodiments, the non-aged distilled alcoholic
spirit is whiskey. In certain embodiments, the non-aged distilled
alcoholic spirit is rum. In certain embodiments, the non-aged
distilled alcoholic spirit is brandy.
[0109] A non-aged distilled alcoholic spirit is typically not
stored for an extended period of time after distillation (e.g., in
oak containers) prior to bottling. Accordingly, in certain
embodiments, a non-aged distilled alcoholic spirit is not stored
after distillation for longer than, e.g., about 3 months, 2 months,
1 month, 3 weeks, 2 weeks, 1 week, 6 days, 5 days, 4 days, 2 days,
1 day, 12 hours or 6 hours prior to bottling. In certain
embodiments, the non-aged distilled alcoholic spirit is not stored
after distillation for longer than about 4 weeks prior to bottling.
In certain embodiments, the non-aged distilled alcoholic spirit is
not stored after distillation prior to bottling. In contrast, an
aged distilled alcoholic spirit will be stored after distillation
(e.g., in oak containers) for a period of time prior to bottling.
Accordingly, in certain embodiments an aged distilled alcoholic
spirit will be stored after distillation (e.g., in oak containers)
as designated per its standard of identity or for at least, e.g.,
about 4 months, 6 months, 8 months, 10 months, 1 year, 2 years, 3
years, 4 years, 5 years, 10 years, 15 years, 20 years, 25 years, 30
years, 40 years or 50 years prior to bottling.
Beer
[0110] Typically, beer refers to ale, porter, stout, or other
similar fermented beverages (including sake' and similar products)
of any name or description containing one-half of one percent or
more of alcohol by volume, brewed or produced from malt, wholly or
in part, or from any substitute for malt. Beer is typically brewed
from malt or from substitutes for malt, such as rice, grain of any
kind, bran, glucose, sugar, and molasses. In addition, the
following materials may be used as adjuncts in fermenting beer:
honey, fruit, fruit juice, fruit concentrate, herbs, spices, and
other such food materials. Additionally, flavors and other
non-beverage ingredients containing alcohol may be used in
producing beer. Generally, flavors and other non-beverage
ingredients containing alcohol contribute no more than 49% of the
overall alcohol content of the finished beer. (see, e.g., 27 C.F.R.
.sctn.25).
[0111] In certain embodiments, the beer has an alcohol by volume of
at least about e.g., 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%,
11%, 12%, 13%, 14% or about 15%.
[0112] Certain embodiments of the invention provide a method of
preparing a modified beer, comprising contacting a corresponding
starting beer with a base under conditions that cause at least one
free carbonyl compound in the starting beer to be reduced, to
provide the modified beer.
[0113] Certain embodiments of the invention provide a method of
preparing a modified beer, comprising contacting a corresponding
starting beer with a base under conditions that cause the total of
free carbonyl compounds in the starting beer to be reduced, to
provide the modified beer.
[0114] In certain embodiments, the pH of the starting beer is about
2.5 to about 5 (e.g., about 3, 3.5, 4, 4.5 or 5).
[0115] In certain embodiments, the pH of the modified beer is about
3 to about 7.5 (e.g., about 3.5, 4, 4.5, 5, 5.5, 6, 6.5 or 7).
[0116] In certain embodiments, the at least one free carbonyl
compound is reduced by at least about 10, 20, 25, 30, 35, 40, 45,
50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by
weight. In certain embodiments, the at least one free carbonyl
compound is reduced by at least about 10% by weight. In certain
embodiments, the at least one free carbonyl compound is reduced by
at least about 20% by weight.
[0117] In certain embodiments, more than one free carbonyl compound
is reduced.
[0118] In certain embodiments, the total of the free carbonyl
compounds is reduced by at least about 10% by weight. Accordingly,
as used herein, the total weight of the free carbonyl compounds in
the starting beer must be reduced by 10% (e.g., certain free
carbonyl species may be reduced while other species may be
unchanged or increased). In certain embodiments, the total of the
free carbonyl compounds is reduced by at least about 20% by weight.
Accordingly, as used herein, the total weight of the free carbonyl
compounds in the starting beer must be reduced by 20% (e.g.,
certain free carbonyl species may be reduced while other species
may be unchanged or increased). In certain embodiments, the total
of the free carbonyl compounds is reduced by at least about 10, 15,
20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96,
97, 98, or 99% by weight.
[0119] In certain embodiments of the invention, the methods further
comprise contacting the starting or modified beer with a carbonyl
scavenger agent (e.g., as described herein).
[0120] Certain embodiments of the invention provide a modified beer
prepared by the methods described herein.
Personal Hygiene Products: Mouthwash
[0121] Mouthwash generally includes liquid oral hygiene and
personal care products that are variously called mouthwashes,
mouth-rinses, oral antiseptics, gargles, fluoride rinses,
anti-plaque rinses, and breath fresheners approved for topical
application. In certain embodiments, a mouthwash does not include
throat sprays or aerosol breath fresheners. Generally, basic
mouthwash ingredients may include water, alcohol, cleansing agents,
flavoring ingredients and/or coloring agents. Depending on the
particular formulation and active ingredients, mouthwash products
may be considered a drug (i.e., its intended use is for preventing
or mitigating disease or to affect the structure or function of the
body, e.g., by preventing cavities, removing plaque and altering
appearance) or a cosmetic (see, e.g., .sctn.201(g) of the Federal
Food, Drug, and Cosmetic Act, 21 U.S.C. 321(g) and 21 C.F.R.
355).
[0122] Certain embodiments of the invention provide a method of
preparing a modified mouthwash comprising providing a corresponding
starting mouthwash with a pH less than about 5.5 and contacting it
with a base to provide a modified mouthwash with a pH greater than
about 6.
[0123] In certain embodiments, the pH of the starting mouthwash is
less than about 5, is less than about 4, or is about 3.
[0124] In certain embodiments, the pH of the modified mouthwash is
greater than about 6, greater than about 7, greater than about 8 or
greater than about 9.
[0125] In certain embodiments, the starting mouthwash has an
alcohol by volume content of at least about 5, 10, 15, 20, 25 or
30%.
[0126] In certain embodiments, at least one free carbonyl compound
in the starting mouthwash is reduced by at least about 10% by
weight. In certain embodiments, at least one free carbonyl compound
in the starting mouthwash is reduced by at least about 20% by
weight or is reduced by at least about 25, 30, 35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by weight.
[0127] In certain embodiments more than one free carbonyl compound
is reduced.
[0128] In certain embodiments, the total of the free carbonyl
compounds in the starting mouthwash is reduced by at least about
10% by weight. In certain embodiments, the total of the free
carbonyl compounds in the starting mouthwash is reduced by at least
about 15% by weight. In certain embodiments, the total of the free
carbonyl compounds in the starting mouthwash is reduced by at least
about 20% by weight or is reduced by at least about 25, 30, 35, 40,
45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by
weight.
[0129] In certain embodiments, the at least one free carbonyl
compound is an aldehyde (e.g, an aldehyde as described herein). In
certain embodiments, the at least one free carbonyl compound is a
ketone (e.g., a ketone as described herein).
[0130] As used herein, a base is a substance (e.g., in a solid or
liquid form) that will increase the pH of the starting mouthwash.
In certain embodiments, the base is a solid. In certain
embodiments, the base is a food grade additive (e.g., has GRAS
status from the FDA). In certain embodiments, the base is sodium
bicarbonate, sodium carbonate, sodium hydroxide, potassium
hydroxide, potassium carbonate or potassium bicarbonate.
[0131] In certain embodiments, the methods further comprise
contacting the starting mouthwash with a carbonyl scavenger
agent.
[0132] In certain embodiments, the methods further comprise
contacting the modified mouthwash with a carbonyl scavenger agent.
In certain embodiments, contacting the modified mouthwash with the
carbonyl scavenger agent causes at least one free carbonyl compound
in the modified mouthwash to be reduced.
[0133] As used herein a carbonyl scavenger agent is a molecular
entity capable of reacting with carbonyls to reduce their free
form. In certain embodiments, the carbonyl scavenger agent is
selected from an alcohol, a sulfite and an amine- or
amide-containing molecule.
[0134] In certain embodiments, the carbonyl scavenger agent is an
alcohol. As used herein alcohol is an organic compound in which the
hydroxyl functional group (--OH) is bound to a saturated carbon
atom. For example, in certain embodiments, the alcohol is a polyol
(i.e., alcohols containing multiple hydroxyl groups). In certain
embodiments, the alcohol is trehalose.
[0135] In certain embodiments the carbonyl scavenger agent is a
sulfite. As used herein a sulfite is a compound that contains the
sulfite ion SO.sub.3.sup.2-. For example, in certain embodiments,
the sulfite is sodium bisulfite.
[0136] In certain embodiments, the carbonyl scavenger agent is an
amine-containing molecule. As used herein, an amine-containing
molecule is an organic compound with a functional group that
contains a basic nitrogen atom with a lone electron pair. Amines
are derivatives of ammonia, wherein one or more hydrogens have been
replaced by an alkyl or aryl group and they can be classified as
primary (R--NH.sub.2), secondary (R, R'--NH), tertiary (R, R',
R''--N) and cyclic amines (R, R', R''--N, wherein R and R' taken
with N forms a ring). As used herein, the term alkyl included both
straight and branched hydrocarbon groups (e.g., a C.sub.1-C.sub.10
alkyl). It is understood that the alkyls can optionally be
substituted. As used herein the term aryl includes a phenyl group
(e.g., radical) and an ortho-fused bicyclic carbocyclic group
(e.g., radical) having about nine to ten ring atoms in which at
least one ring is aromatic. It is understood that the aryls can
optionally be substituted. For example, in certain embodiments, the
amine-containing molecule is an anthranilite (e.g., methyl
anthranilite). In certain embodiments, the amine-containing
molecule is monosodium glutamate.
[0137] In certain embodiments, the carbonyl scavenger agent is an
amide-containing molecule. As used herein, an amide-containing
molecule is a small organic molecule that includes a --C(.dbd.O)N
moiety. In one embodiment, the amide comprises 1-20 carbon atoms.
In one embodiment, the amide comprises 1-10 carbon atoms. In
certain embodiments, the amide may be cyclic or linear. For
example, in certain embodiments, the amide is selected from
lactamide, acetamide and butyramide. In certain embodiments, the
amide is butyramide.
[0138] In certain embodiments, the carbonyl scavenger agent is a
food grade additive (e.g., has GRAS status from the FDA).
[0139] In certain embodiments, the carbonyl scavenger agent is
bound to a polymer (e.g., silica). In certain embodiments, the
polymer bound scavenger agent is removed by, e.g., filtration. In
certain embodiments, polymer bound scavenger reaction by-products
(i.e., the scavenger agent bound to a carbonyl) are removed by,
e.g., filtration.
[0140] In certain embodiments, the carbonyl scavenger agent is a
polymer bound sulfonyl hydrazine.
[0141] In certain embodiments, the carbonyl scavenger is a polymer
bound tosyl hydrazine.
[0142] In certain embodiments, the at least one free carbonyl
compound in the starting mouthwash is reduced by at least about 10%
by weight in, e.g., two weeks (i.e., two weeks from when the
starting mouthwash is contacted by the base). In certain
embodiments, the at least one free carbonyl compound in the
starting mouthwash is reduced by at least about 10% by weight in,
e.g., about 1 week, 6 days, 5, days, 4 days, 3 days, 2 days, 1 day,
12 hours, 6 hours, 3 hours.
[0143] In certain embodiments, the at least one free carbonyl
compound in the starting mouthwash is reduced by at least about 20%
by weight in, e.g., two weeks (i.e., two weeks from when the
starting mouthwash is contacted by the base). In certain
embodiments, the at least one free carbonyl compound in the
starting mouthwash is reduced by at least about 20% by weight in,
e.g., about 1 week, 6 days, 5, days, 4 days, 3 days, 2 days, 1 day,
12 hours, 6 hours, 3 hours.
[0144] In certain embodiments, the total of the free carbonyl
compounds in the starting mouthwash is reduced by at least about
10% by weight in, e.g., two weeks (i.e., two weeks from when the
starting mouthwash is contacted by the base). In certain
embodiments, the total of the free carbonyl compounds in the
starting mouthwash is reduced by at least about 10% by weight in,
e.g., about 1 week, 6 days, 5 days, 4 days, 3 days, 2 days, 1 day,
12 hours or 6 hours.
[0145] In certain embodiments, the total of the free carbonyl
compounds in the starting mouthwash is reduced by at least about
20% by weight in, e.g., two weeks (i.e., two weeks from when the
starting mouthwash is contacted by the base). In certain
embodiments, the total of the free carbonyl compounds in the
starting mouthwash is reduced by at least about 20% by weight in,
e.g., about 1 week, 6 days, 5 days, 4 days, 3 days, 2 days, 1 day,
12 hours or 6 hours.
[0146] In certain embodiments, the trigeminal ethanol related burn,
smoothness, taste, aroma and/or flavor profile of the modified
mouthwash is improved over the starting mouthwash. In certain
embodiments, the improvement may be determined by a subject
sampling the modified and starting mouthwashes and rating the
mouthwashes using sensory techniques, such as the degree of
difference test or descriptive analysis (see, e.g., the
Examples).
[0147] Certain embodiments of the invention provide a modified
mouthwash prepared by the methods described herein.
[0148] Certain embodiments of the invention provide a mouthwash
comprising less than 0.1% by weight free carbonyl compounds. In
certain embodiments, the mouthwash comprises less than, e.g., about
0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 0.009, 0.008,
0.007, 0.006, 0.005, 0.004, 0.003, 0.002, 0.001, 0.0009, 0.0008,
0.0007, 0.0006, 0.0005, 0.0004, 0.0003, 0.0002 or 0.0001% by weight
free carbonyl compounds. It is to be understood that the percent by
weight of free carbonyl compounds refers to the total weight of the
free carbonyl compounds in the mouthwash. In certain embodiments,
the mouthwash has an alcohol by volume content of at least about 5,
10, 15, 20, 25 or 30%.
[0149] Certain embodiments of the invention provide a modified
mouthwash (e.g., a mouthwash prepared accordingly to a method
described herein, e.g., a mouthwash that has been contacted by a
base) comprising at least one free carbonyl compound, wherein the
at least one free carbonyl compound is reduced as compared to a
corresponding unmodified mouthwash (e.g., a mouthwash that has not
been prepared by a method described herein). In certain
embodiments, the modified mouthwash has an alcohol by volume
content of at least about 5, 10, 15, 20, 25 or 30%.
[0150] Certain embodiments of the invention provide a modified
mouthwash comprising free carbonyl compounds, wherein the total of
the free carbonyl compounds are reduced as compared to the total of
free carbonyl compounds in a corresponding unmodified mouthwash. In
certain embodiments, the modified mouthwash has an alcohol by
volume content of at least about 5, 10, 15, 20, 25 or 30%.
[0151] In certain embodiments, the at least one free carbonyl
compound in the modified mouthwash is reduced by at least about 10,
20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96,
97, 98, or 99% by weight as compared to a corresponding unmodified
mouthwash. In certain embodiments, the at least one free carbonyl
compound in the modified mouthwash is reduced by at least about 10%
by weight as compared to a corresponding unmodified mouthwash. In
certain embodiments, the at least one free carbonyl compound in the
modified mouthwash is reduced by at least about 20% by weight as
compared to a corresponding unmodified mouthwash.
[0152] In certain embodiments, more than one free carbonyl compound
is reduced.
[0153] In certain embodiments, the total of the free carbonyl
compounds in the modified mouthwash is reduced by at least about
10% by weight as compared to the total of free carbonyl compounds
in a corresponding unmodified mouthwash. Accordingly, as used
herein, the total weight of the free carbonyl compounds in the
modified mouthwash must be reduced by 10% (e.g., certain free
carbonyl species may be reduced while other species may be
unchanged or increased). In certain embodiments, the total of the
free carbonyl compounds in the modified mouthwash is reduced by at
least about 20% by weight as compared to the total of free carbonyl
compounds in a corresponding unmodified mouthwash. Accordingly, as
used herein, the total weight of the free carbonyl compounds in the
modified mouthwash must be reduced by 20% (e.g., certain free
carbonyl species may be reduced while other species may be
unchanged or increased). In certain embodiments, the total of the
free carbonyl compounds is reduced by at least about 10, 15, 25,
30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98,
or 99% by weight as compared to the total of free carbonyl
compounds in the unmodified mouthwash.
[0154] Certain embodiments of the invention provide a mouthwash
with a pH greater than about 6 (e.g., greater than about 6, 7, 8 or
9) and an alcohol by volume content of at least 5%. In certain
embodiments, the mouthwash has improved trigeminal ethanol related
burn, smoothness, taste, aroma and/or flavor profile in comparison
to a corresponding mouthwash with a pH less than about 6 (e.g.,
less than about 6, 5.5, 5, 4.5, 4, 3.5 or 3) and an alcohol by
volume content of at least 5%.
Alcohol Containing Medicaments
[0155] Certain embodiments of the invention provide a method of
preparing a modified medicament comprising providing a
corresponding starting medicament with a pH less than about 5 and
contacting it with a base to provide a modified medicament with a
pH greater than about 6, wherein the modified medicament has an
alcohol by volume of at least 5%.
[0156] In certain embodiments, the pH of the starting medicament is
less than about 6, is less than about 5, is less than about 4, less
than about 3 or less than about 2.
[0157] In certain embodiments, the pH of the modified medicament is
greater than about 6, greater than about 7, greater than about 8 or
greater than about 9.
[0158] In certain embodiments, the modified medicament has an
alcohol by volume content of at least about 5, 10, 15, 20, 25, 30,
35, 40 or 45%.
[0159] In certain embodiments, the starting medicament comprises at
least one of a cough suppressant, an expectorant, a pain reliever,
a fever reducer agent, an analgesic agent, a vasodilator agent, an
antihistamine or an antispasmodic agent.
[0160] In certain embodiments, the medicament comprises a cough
medicine. In certain embodiments, the medicament comprises an
expectorant. In certain embodiments the medicament comprises a pain
reliever and/or fever reducer. In certain embodiments, the
medicament comprises an analgesic agent. In certain embodiments the
medicament comprises a vasodilator. In certain embodiments the
medicament comprises an antihistamine. In certain embodiments the
medicament comprises an antispasmodic.
[0161] In certain embodiments, at least one free carbonyl compound
in the starting medicament is reduced, e.g., is reduced by at least
about 10% by weight. In certain embodiments, at least one free
carbonyl compound in the starting medicament is reduced, e.g., is
reduced by at least about 15% by weight. In certain embodiments, at
least one free carbonyl compound in the starting medicament is
reduced, e.g., is reduced by at least about 20% by weight, or at
least about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90,
95, 96, 97, 98, or 99% by weight. In certain embodiments, more than
one free carbonyl compound is reduced.
[0162] In certain embodiments, the total of the free carbonyl
compounds in the starting medicament is reduced, e.g., reduced by
at least about 10% by weight. In certain embodiments, the total of
the free carbonyl compounds in the starting medicament is reduced,
e.g., reduced by at least about 15% by weight. In certain
embodiments, the total of the free carbonyl compounds in the
starting medicament is reduced, e.g., reduced by at least about 20%
by weight or is reduced by at least about 25, 30, 35, 40, 45, 50,
55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% by
weight.
[0163] In certain embodiments, the at least one free carbonyl
compound is an aldehyde (e.g., as described herein). In certain
embodiments, the at least one free carbonyl compound is a
ketone.
[0164] As used herein, a base is a substance (e.g., in a solid or
liquid form) that will increase the pH of the starting medicament.
In certain embodiments, the base is a solid. In certain
embodiments, the base is a liquid. In certain embodiments, the base
is a food grade additive (e.g., has GRAS status from the FDA). In
certain embodiments, the base is sodium bicarbonate, sodium
carbonate, sodium hydroxide, potassium carbonate, potassium
bicarbonate or potassium hydroxide.
[0165] In certain embodiments, the methods further comprise
contacting the starting medicament with a carbonyl scavenger
agent.
[0166] In certain embodiments, the methods further comprise
contacting the modified medicament with a carbonyl scavenger agent.
In certain embodiments, contacting the modified medicament with the
carbonyl scavenger agent causes at least one free carbonyl compound
in the modified medicament to be reduced.
[0167] As used herein a carbonyl scavenger agent is a molecular
entity capable of reacting with carbonyls to reduce their free
form. In certain embodiments, the carbonyl scavenger agent is
selected from an alcohol, a sulfite and an amine- or
amide-containing molecule.
[0168] In certain embodiments, the carbonyl scavenger agent is an
alcohol. As used herein alcohol is an organic compound in which the
hydroxyl functional group (--OH) is bound to a saturated carbon
atom. For example, in certain embodiments, the alcohol is a polyol
(i.e., alcohols containing multiple hydroxyl groups). In certain
embodiments, the alcohol is trehalose.
[0169] In certain embodiments the carbonyl scavenger agent is a
sulfite. As used herein a sulfite is a compound that contains the
sulfite ion SO.sub.3.sup.2-. For example, in certain embodiments,
the sulfite is sodium bisulfite.
[0170] In certain embodiments, the carbonyl scavenger agent is an
amine-containing molecule. As used herein, an amine-containing
molecule is an organic compound with a functional group that
contains a basic nitrogen atom with a lone electron pair. Amines
are derivatives of ammonia, wherein one or more hydrogens have been
replaced by an alkyl or aryl group and they can be classified as
primary (R--NH.sub.2), secondary (R, R'--NH), tertiary (R, R',
R''--N) and cyclic amines (R, R', R''--N, wherein R and R' taken
with N forms a ring). As used herein, the term alkyl included both
straight and branched hydrocarbon groups (e.g., a C.sub.1-C.sub.10
alkyl). It is understood that the alkyls can optionally be
substituted. As used herein the term aryl includes a phenyl group
(e.g., radical) and an ortho-fused bicyclic carbocyclic group
(e.g., radical) having about nine to ten ring atoms in which at
least one ring is aromatic. It is understood that the aryls can
optionally be substituted. For example, in certain embodiments, the
amine-containing molecule is an anthranilite (e.g., methyl
anthranilite). In certain embodiments, the amine-containing
molecule is monosodium glutamate.
[0171] In certain embodiments, the carbonyl scavenger agent is an
amide-containing molecule. As used herein, an amide-containing
molecule is a small organic molecule that includes a --C(.dbd.O)N
moiety. In one embodiment, the amide comprises 1-20 carbon atoms.
In one embodiment, the amide comprises 1-10 carbon atoms. In
certain embodiments, the amide may be cyclic or linear. For
example, in certain embodiments, the amide is selected from
lactamide, acetamide and butyramide. In certain embodiments, the
amide is butyramide.
[0172] In certain embodiments, the carbonyl scavenger agent is a
food grade additive (e.g., has GRAS status from the FDA).
[0173] In certain embodiments, the carbonyl scavenger agent is
bound to a polymer (e.g., silica). In certain embodiments, the
polymer bound scavenger agent is removed by, e.g., filtration. In
certain embodiments, polymer bound scavenger reaction by-products
(e.g, scavenger agent bound to a carbonyl) are removed by, e.g.,
filtration.
[0174] In certain embodiments, the carbonyl scavenger agent is a
polymer bound sulfonyl hydrazine.
[0175] In certain embodiments, the carbonyl scavenger is a polymer
bound tosyl hydrazine.
[0176] In certain embodiments, the at least one free carbonyl
compound in the starting medicament is reduced by at least about
10% by weight in, e.g., two weeks (i.e., two weeks from when the
starting medicament is contacted by the base). In certain
embodiments, the at least one free carbonyl compound in the
starting medicament is reduced by at least about 10% by weight in,
e.g., 1 week, 6 days, 5, days, 4 days, 3 days, 2 days, 1 day, 12
hours or 6 hours.
[0177] In certain embodiments, the at least one free carbonyl
compound in the starting medicament is reduced by at least about
20% by weight in, e.g., two weeks (i.e., two weeks from when the
starting medicament is contacted by the base). In certain
embodiments, the at least one free carbonyl compound in the
starting medicament is reduced by at least about 20% by weight in,
e.g., 1 week, 6 days, 5, days, 4 days, 3 days, 2 days, 1 day, 12
hours or 6 hours.
[0178] In certain embodiments, the total of the free carbonyl
compounds in the starting medicament is reduced by at least about
10% by weight in, e.g., about two weeks (i.e., two weeks from when
the starting medicament is contacted by the base). In certain
embodiments, the total of the free carbonyl compounds in the
starting medicament is reduced by at least about 10% by weight in,
e.g., about 1 week, 6 days, 5, days, 4 days, 3 days, 2 days, 1 day,
12 hours or 6 hours.
[0179] In certain embodiments, the total of the free carbonyl
compounds in the starting medicament is reduced by at least about
20% by weight in, e.g., about two weeks (i.e., two weeks from when
the starting medicament is contacted by the base). In certain
embodiments, the total of the free carbonyl compounds in the
starting medicament is reduced by at least about 20% by weight in,
e.g., about 1 week, 6 days, 5, days, 4 days, 3 days, 2 days, 1 day,
12 hours or 6 hours.
[0180] In certain embodiments, the trigeminal ethanol related burn,
smoothness, taste, aroma and/or flavor profile of the modified
medicament is improved over the starting medicament. In certain
embodiments, the improvement may be determined by a subject
sampling the modified and starting medicaments and rating the
medicaments using sensory techniques, such as the degree of
difference test or descriptive analysis (see, e.g., the
Examples).
[0181] Certain embodiments of the invention provide a modified
medicament prepared by the methods described herein.
[0182] Certain embodiments of the invention provide a medicament
comprising less than 0.1% by weight free carbonyl compounds,
wherein the medicament has an alcohol by volume of at least 5%. In
certain embodiments the medicament comprises less than, e.g., about
0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, 0.01, 0.009, 0.008,
0.007, 0.006, 0.005, 0.004, 0.003, 0.002, 0.001, 0.0009, 0.0008,
0.0007, 0.0006, 0.0005, 0.0004, 0.0003, 0.0002 or 0.0001% by weight
free carbonyl compounds. It is to be understood that the percent by
weight of free carbonyl compounds refers to the total weight of the
free carbonyl compounds in the medicament.
[0183] Certain embodiments of the invention provide a modified
medicament (e.g., a medicament that has been prepared by a method
described herein, e.g., a medicament that has been contacted by a
base) comprising at least one free carbonyl compound, wherein the
modified medicament has an alcohol by volume of at least 5%; and
wherein the at least one free carbonyl compound is reduced as
compared to a corresponding unmodified medicament (e.g., a
medicament that has not been prepared by a method described
herein).
[0184] Certain embodiments of the invention provide a modified
medicament (e.g., a medicament that has been contacted by a base)
comprising free carbonyl compounds, wherein the modified medicament
has an alcohol by volume of at least 5%; and wherein the total of
the free carbonyl compounds are reduced as compared to the total of
free carbonyl compounds in a corresponding unmodified
medicament.
[0185] In certain embodiments, the at least one free carbonyl
compound in the modified medicament is reduced by at least about
10, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,
96, 97, 98, or 99% by weight as compared to a corresponding
unmodified medicament. In certain embodiments, the at least one
free carbonyl compound in the modified medicament is reduced by at
least about 10% by weight as compared to a corresponding unmodified
medicament. In certain embodiments, the at least one free carbonyl
compound in the modified medicament is reduced by at least about
20% by weight as compared to a corresponding unmodified
medicament.
[0186] In certain embodiments, more than one free carbonyl compound
is reduced.
[0187] In certain embodiments, the total of the free carbonyl
compounds in the modified medicament is reduced by at least about
10% by weight as compared to the total of free carbonyl compounds
in a corresponding unmodified medicament. Accordingly, as used
herein, the total weight of the free carbonyl compounds in the
modified medicament are be reduced by 10% (e.g., certain free
carbonyl species may be reduced while other species may be
unchanged or increased). In certain embodiments, the total of the
free carbonyl compounds in the modified medicament is reduced by at
least about 20% by weight as compared to the total of free carbonyl
compounds in a corresponding unmodified medicament. Accordingly, as
used herein, the total weight of the free carbonyl compounds in the
modified medicament are be reduced by 20% (e.g., certain free
carbonyl species may be reduced while other species may be
unchanged or increased). In certain embodiments, the total of the
free carbonyl compounds is reduced by at least about 10, 15, 20,
25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97,
98, or 99% by weight as compared to the total of free carbonyl
compounds in the unmodified medicament.
[0188] Certain embodiments of the invention provide a medicament
with a pH greater than about 5 (e.g., greater than about 6, 7, 8 or
9) and an alcohol by volume content of at least 5% (e.g., at least
10%, 15%, 20% or more). In certain embodiments, the medicament has
improved trigeminal ethanol related burn, smoothness, taste, aroma
and/or flavor profile in comparison to a corresponding medicament
with a pH less than about 5 and an alcohol by volume content of at
least 5%.
[0189] In certain embodiments, the medicament comprises at least
one of a cough suppressant, an expectorant, a pain reliever, a
fever reducer agent, an analgesic agent, a vasodilator agent, an
antihistamine or an antispasmodic agent.
[0190] The invention will now be illustrated by the following
non-limiting Examples.
Example 1
[0191] Smoothness and maturity of alcoholic beverages are general
descriptors that are predominately correlated with higher
palatability and consumer preference. In general, sensory changes
that occur during maturation include changes in sourness,
astringency, trigeminal burning sensation intensity and the
mouth-feel. In general the chemical drivers of alcohol burn is not
well defined.
[0192] Smoothness and maturity are desirable sensory traits and
understanding the chemical drivers of those sensations may
facilitate the development of ingredient or processing technologies
that will allow improved palatability of a wide range of alcoholic
products, including alcoholic beverages and spirits, alcohol
containing personal hygiene products such as mouthwash and
pharmaceutical products such as cough syrups etc. Understanding the
chemical drivers of flavor perception of aqueous/ethanol systems
would reveal the chemistry of smoothness and maturation perception
and thus opportunities for a wide platform of alcoholic product
optimization.
[0193] Most studies on alcoholic products thus far have focused on
changes of volatile markers (aldehydes, ketones, esters, lactones,
fusel oils etc.) during production as well as maturation-storage
(depending on product) and their effect on aroma. Little is known
as to how changes affect trigeminal sensation. As described herein,
it has now been shown that these species undoubtedly impact the
perception of trigeminal burn and consequently the smoothness and
maturation.
[0194] It has been suggested that the equilibrium between
aldehydes, ketones, alcohols, hemiacetals and acetals is altered in
distilled spirits and alcoholic beverages (Perry, D R 1986: Whisky
maturation mechanisms. In Proc. 2nd Aviemore Conf. Malt. Brew).
Aldehydes have been associated with pungent, sharp aromas as well
as bitterness and astringency and acetals are more pleasant and
fruity (Russell I., Stewart G., Whisky: Technology, Production and
Marketing 2003, Elsevier Ltd.; Perry, D R 1989: Odour intensities
of whisky compounds. In Distilled Beverage flavor: Recent
developments. Piggot, J R and Paterson, A. Ellis Horwood,
Chichester, UK, pp 200-207) and it has been observed that their
concentration can be affected by intrinsic pH of the product
(during maturation) and ethanol levels.
Materials and Methods
[0195] pH Modulation.
[0196] In an effort to examine the effect of pH modification on the
sensory properties of aqueous/alcoholic systems a 60% water 40%
ethanol solution was chosen as a representative model of distilled
alcoholic beverages. The pH of that system was adjusted from 6.30
to either 3.00 or 8.00, the samples were subsequently stored for 24
hrs, and sensory and carbonyl species changes were qualitatively
and quantitatively determined. The pH was adjusted with using
phosphoric acid for the acidic range and sodium hydroxide for the
basic range. Sensory properties of the resulted samples were
examined employing a degree of difference test. The effect of the
different pH modifiers on the levels of carbonyl species was also
determined using the above-mentioned dynamic headspace GC/MS
method.
[0197] The sensory effect of pH modification of commercially
available alcoholic products was such as vodka, brandy and
mouthwash was also similarly examined.
[0198] Carbonyls Species Fingerprint and Quantification.
[0199] Sample Preparation.
[0200] As a concentration step and in order to optimize our
analytical method for carbonyl species quantification in
aqueous-alcoholic products, sodium bisulfite was utilized as a
carbonyl scavenger. Sodium bisulfite is known to react with
aldehydes and ketones and form bisulfite adducts, as shown in
Scheme 1, which then precipitate and are easily isolated via
filtration.
##STR00001##
The advantage of this reaction is its reversibility, as shown in
Scheme 2. Addition of a base such as sodium bicarbonate or sodium
hydroxide results in regeneration of carbonyl species.
##STR00002##
Based on this reaction scheme a method coupling carbonyl
scavenging, dynamic headspace and GC/MS was developed for carbonyl
species quantification. Method details can be seen in FIG. 1.
[0201] Dynamic Headspace GC/MS-Scan and SIM.
[0202] An automated dynamic headspace (DHS) method was developed
for the identification and quantification of aldehydes, ketones,
acetals/hemiacetals and fusel oils. Analysis was performed using a
6890 GC equipped with a 5973 Mass Selective Detector (Agilent
Technologies), Thermal Desorption Unit (TDU, Gerstel), PTV inlet
(CIS 4, Gerstel) and MPS 2 with headspace and DHS option (Gerstel).
A highly inert CP-SIL 5CB GC column, which withstands large solvent
injections, (desirable due to the high ethanol content of our
samples) was used for chromatographic separation. The method was
optimized and the analysis and dynamic headspace conditions are
reported in Tables 1 and 2 respectively.
[0203] Aqueous samples can often be problematic for headspace
analysis. The presence of water vapor in the headspace above the
sample can lead to poor analytical precision. Operating the PTV
inlet in solvent vent mode significantly reduced the amount of
water transferred to the analytical column. The DHS system enabled
dynamic purging of the headspace above a sample and trapping onto
tenax TA traps, a dry purge reduced the water content. The thermal
desorption tube was then placed into the Thermal Desorption Unit
(TDU) and thermally desorbed into the pre-cooled CIS 4 inlet, where
the analytes were cryofocused to improve peak shape before
introduction into the GC column.
[0204] The mass spectrometer was operated under scan mode when
sodium bisulfite was used as a concentration step.
TABLE-US-00001 TABLE 1 Column information and Inlet and GC oven
operating parameters employed for chromatographic separation of
analytes of interest. Analysis conditions PTV Tenax TA liner,
solvent vent (60 mL/min) at 0 kPa splitless (2 min), 20.degree. C.
(0.2 min); 10.degree. C./s; 300.degree. C. (5 min) Column 25 m
CP-SIL 5CB 0.15 mm .times. 2.0 .mu.m He, constant flow = 0.5 mL/min
Oven 40.degree. C. (10 min); 10.degree. C./min; 280.degree. C. (6
min) MSD Scan, 28-350 amu* *When Mass Spectrometer was operated in
scan mode
TABLE-US-00002 TABLE 2 Optimized dynamic headspace (DHS) and
thermal desorption (TDU) flow and temperature profiles employed for
trapping and injecting analytes of interest. Dynamic headspace DHS
conditions Chemical Tenax TA trap DHS 30.degree. C. trap
temperature, 60.degree. C. inc temperature (10 min) 50 mL purge
volume, 10 mL/min purge flow 10 mL dry volume, 5 mL/min dry flow
TDU solvent venting 20.degree. C. (1 min); 720.degree. C./min;
110.degree. C. (1 min); 720.degree. C./min; 300.degree. C. (3
min)
An optimized automated dynamic headspace (DHS) GC/MS-SIM method was
also developed and employed for the analysis of alcoholic products
with varying percentages of ethanol, allowing for improved
sensitivity with no sample concentration step. Analysis and dynamic
headspace conditions and MS SIM parameters are reported in Tables
3, 4 and 5. Briefly, 1 mL of sample (40% ethanol content) was
placed in a 20 mL headspace vial and diluted with nanopure water to
final volume of 10 mL. Methyl hexanoate was added as an internal
standard (10 .mu.g).
TABLE-US-00003 TABLE 3 Column information and Inlet and GC oven
operating parameters employed for chromatographic separation of
analytes of interest. Analysis conditions PTV Tenax TA liner,
solvent vent (30 mL/min) at 0 kPa splitless (0.5 min), 20.degree.
C. (0.5 min); 10.degree. C./s; 300.degree. C. (5 min) Column 25 m
CP-SIL 5CB 0.15 mm .times. 2.0 .mu.m He, constant flow = 0.5 mL/min
Oven 40.degree. C. (10 min); 10.degree. C./min; 280.degree. C. (5
min) MSD SIM
TABLE-US-00004 TABLE 4 Optimized dynamic headspace (DHS) and
thermal desorption (TDU) flow and temperature profiles employed for
trapping and injecting analytes of interest. Dynamic headspace DHS
conditions Chemical trap Tenax TA DHS 30.degree. C. trap
temperature, 55.degree. C. incubation temp (12 min) 2000 mL purge
volume, 16 mL/min purge flow 30 mL dry volume, 7 mL/min dry flow
TDU solvent venting 20.degree. C. (0.80 min); 720.degree. C./min;
110.degree. C. (1 min); 720.degree. C./min; 300.degree. C. (4
min)
TABLE-US-00005 TABLE 5 MS/single ion monitoring (SIM) parameters
employed for quantification of chemical species of interest.
Compound m/z ions Acetal 45, 73, 103 Hexanal 56, 72, 82 2-heptanone
58, 71, 114 Heptanal 55, 96, 114 Methyl 74, 87, 99 hexanoate
Benzaldehyde 77, 105, 106 Octanal 57, 69, 84 Nonanal 57, 70, 98
Decanal 57, 95, 112
In order to examine and confirm as predicted that the observed
differences on carbonyl species quantified (by headspace analysis)
between samples with different pH values were not the result of
altered volatility of the carbonyl compounds themselves (due to pH
changes) 200 ml of water with pH adjusted to either 3.00 or 8.00
was spiked with 10 ppm of butanal, hexanal, heptanal, octanal,
nonanal, decanal and benzaldehyde and carbonyls species were
quantified via Headspace GC/MS.
[0205] Si-Tosyl hydrazine (230-400 mesh) and sulfonyl hydrazine
(30-60 mesh) with a loading capacity of 0.8 mmol/g and 1.6-3 mmol/g
respectively were used. The mechanism of the trapping reaction
between the polymer hydrazines and carbonyl species is presented in
FIG. 2, along with the structure of the scavengers used. The
experimental protocol followed for sample preparation prior to
sensory analysis is illustrated in FIG. 3.
[0206] Trehalose.
[0207] Trehalose, a food grade naturally occurring disaccharide was
employed due to structure reactivity towards trapping carbonyl
species (presence of hydroxyl--reactive nucleophiles known to react
with carbonyl species such as aldehydes and ketones). Trehalose was
incorporated in relatively low levels (0.2%). Sensory evaluation
was conducted after 24, 48 and 72 hrs.
[0208] Sodium Bisulfite.
[0209] Sodium bisulfite was examined as potential ingredient
treatment as it reacts with carbonyl species to form adducts. It is
a GRAS ingredient and it is commonly added in wine and beer to
prevent yeast growth. Two levels of sodium bisulfite were utilized,
namely 200 and 1000 ppm (mg/L). Employed levels were chosen based
on commonly used concentration of sulfites in winemaking and were
well within allowable limits (100-200 ppm of SO.sub.2 in solution).
Sensory evaluation was conducted after 24, 48 and 72 hrs.
[0210] Anthranilites.
[0211] This group of chemicals was explored as a potential
treatment due to structure reactivity (Scheme 3) towards trapping
carbonyl species (presence of amine group-reactive nucleophiles
known to react with carbonyl species such as aldehydes and
ketones). Methyl, ethyl, cinnamyl and isobutyl anthranilites were
tested and were incorporated in relatively low levels (5 ppm).
Sensory evaluation was conducted after 24, 48 and 72 hrs.
##STR00003##
[0212] Amides.
[0213] This class of compounds was selected as a potential
treatment again due the potential trapping reactivity towards
carbonyl species as the amide group present can act a nucleophile
and react with the electrophilic carbonyl carbon of aldehydes and
ketones. The following five amide compounds were explored as
potential treatments and added at levels of 50 mg/L: Lactamide,
2-hydroxyethyl lactamide, 2-hydroxyethyl propionamide,
N,N'-bis(2-hydroxyethyl)oxamide and butyramide. Sensory evaluation
was conducted after 24, 48 and 72 hrs.
[0214] .sup.1H NMR for Analysis of Alcoholic Beverages.
[0215] Nuclear magnetic resonance (NMR) spectroscopy was used to
analyzed chemical fingerprint of different vodkas and the effect of
pH modification on carbonyl species in Karkov. NMR spectra
collection was performed as described by Monakhova, et al., Magn.
Reson. Chem., 2011, 49, 734-739. Code was developed and optimized
for signal suppression of both ethanol and water and a Bruker 700
Ultrashield (5 mm TXI 700 MHz Z-Gradient). For sample preparation
two buffer systems were used to accommodate the pH of vodka
samples. Buffer 1 had a pH of 7.4, consisted of 1.5 M monopotassium
phosphate KH.sub.2PO.sub.4 in deuterated water D.sub.2O, 0.1%
3-(trimethylsilyl)-propionateacid-d4 (TSP), 3 mM Sodium Azide
(NaN.sub.3). Buffer 1 was utilized for sample preparation and data
collection of pH modified Karkov (pH 8.00). Buffer 2 had a pH of
2.5, consisted of 1.5 M monopotassium phosphate (KH.sub.2PO.sub.4
in deuterated water D.sub.2O, 0.1%
3-(trimethylsilyl)-propionateacid-d4 (TSP). Buffer 2 was utilized
for sample preparation and spectra collection of original Karkov
samples (pH 3.00). Data was processed and handled using
TopSpin.
[0216] Sensory Analysis.
[0217] For sensory evaluation, six panelists were selected based on
product usage and familiarity, discrimination ability and task
comprehension. The panelists have been trained with a "smoothness"
(trigeminal burn) reference scale consisting of solutions of pure
food grade ethanol: nanopure water (40:60) without and with added
glycerin at levels of 0.2, 0.5, 1 and 2% in order to familiarize
with the sensory attributes of interest (i.e. trigeminal burn).
[0218] Degree-of-difference tests were used to estimate the
difference of trigeminal burn intensity between the control samples
and treated samples (pH modified and/or carbonyl scavenger
treated). A 15-point linear scale was used to indicate differences
in trigeminal burn of the samples ranging from no difference (0) to
extremely different (15). A positive and a negative scale were used
to capture both possible directional changes. A negative rating was
used when the trigeminal burn intensity decreased whereas a
positive value indicated an increase in trigeminal burn intensity.
All samples were presented with 3-digit randomized codes at room
temperature and panelists with and without nose clips during
evaluation.
[0219] Three different commercial alcoholic products were included
for sensory evaluation, namely vodka, brandy and mouthwash and a
water/ethanol model system comprised of 60% nanopure water and 40%
food grade ethanol in order to determine the sensory effect pH
modification and carbonyl species in alcohol perception, smoothness
and maturation. In order to further examine causality, the effect
of the carbonyl concentration on smoothness (i.e. trigeminal burn)
was also determined by evaluating samples with added carbonyl
compounds.
Results and Discussion
[0220] Dynamic headspace analysis of water/ethanol (60/40) with pH
6.3 and modified pH samples at pH 3.0 and 8.0 revealed a
significant difference in the content of carbonyl species. The
chromatograms obtained from samples with pH 3.0 had higher numbers
of aldehydes, as well as the concentrations were increased when
compared to Karkov with pH 8.0. Increased pH resulted in
significant reduction of aldehydes such as butanal, pentanal,
hexanal, heptanal, octanal, nonanal, decanal and benzaldehyde. The
observed difference between samples in content of carbonyl species
was, in some cases (i.e. nonanal, decanal), upwards of 4-fold (see
FIG. 4).
[0221] Sensory evaluation of these samples was also conducted in
order to confirm the correlation between decreased levels of
aldehydes and improved alcohol smoothness perception. Panelists
were asked to rank the water/ethanol solutions with pH of 3.0, 6.3
and 8.0 utilizing a difference from control scale using
water/ethanol solution with pH of 6.3 as control. Results shown in
Table 6 further support the negative effect of the presence of
aldehyde in smoothness perception of water/alcohol which supports
our initial hypothesis and suggests that a strong correlation
exists between concentration of carbonyl species in distilled
spirits and flavor perception and consumer acceptability.
TABLE-US-00006 TABLE 6 Average (n = 6) degree of difference ratings
for trigeminal burn of water/ethanol solution (60/40) with and
without pH modification. Sample Rating.sup.1 Water/ethanol (pH 6.3)
(Blind Control) 0.75.sup.a Water/ethanol (pH 3.0) 8.40.sup.b
Water/ethanol (pH 8.0) -4.10.sup.c .sup.1Different letters indicate
statistically significant difference determined by one-way ANOV
analysis and Dunnetts test (.alpha. = 0.05); .sup.anot
significantly different than control.
[0222] Quantification of carbonyl species of a water/ethanol
solution at pH 6.3 that was treated with sulfonyl hydrazine resin
(carbonyl scavenger) was performed and compared to samples with no
sulfonyl hydrazine treatment and the results are presented in FIG.
5. Sulfonyl hydrazine was shown to be effective in reducing
carbonyls levels as reduction after treatment ranged between
20-73%. Sensory evaluation of these samples was also conducted.
Panelists were asked to rank the 2 water/ethanol samples based on
increasing smoothness and the following order was revealed:
Water/Ethanol pH 6.3<Water/Ethanol pH 6.3 Sulfonyl-hydrazine
treated further supporting that carbonyl species appear to greatly
influence smoothness, trigeminal burning sensation and the overall
flavor quality of water/ethanol solution.
[0223] In order to confirm that increased amounts of aldehydes in
these samples negatively affect smoothness perception and increase
burn intensity, samples were prepared with higher levels of
aldehydes (added 5 ppm each) and immediately the panelists were
asked to rank them based on increasing smoothness: water/ethanol
(pH 3.0), water/ethanol (pH 8.0), water/ethanol (pH 3.0) with
spiked aldehydes (5 ppm) and water/ethanol (pH 8.0) with spiked
aldehydes (5 ppm). During sensory evaluation nose clips were used
as to avoid the contribution of aroma in smoothness perception and
to establish the trigeminal effect of aldehydes in alcohol
perception. Panelists placed the samples in the following order of
increasing smoothness (lowest was on the left to highest on the
right): water/ethanol (pH 3.0)+5 ppm aldehydes<water/ethanol (pH
8.0)+5 ppm aldehydes <water/ethanol (pH 3.0)<water/ethanol
(pH 8.0). These results support the findings that increased
concentration of aldehydes are highly influential to the flavor
profile of aqueous/ethanol products, making them an important
target for flavor improvement technologies. After approximately 48
hrs panelists were asked to evaluate the samples again and this
time the modified water/ethanol (pH 8)+5 ppm was perceived as
smoother than water/ethanol (pH 3.00) demonstrating again that pH
adjustment is critical in alcohol modulation and trigeminal
sensation. This also confirms that this chemistry can be
potentially applied in the general platform of aqueous/ethanol
products (beverages, pharmaceutical and personal hygiene) for
alcohol perception modulation and improvement of sensory and
organoleptic properties. The pH effects on the concentration of
carbonyl species in ethanol solutions were noted to be time
dependent and typically within a few hours quantitative changes in
the carbonyl concentrations were observed.
[0224] In order to confirm that the observed differences in the
carbonyl load quantified between the pH modified products are not
the result of a sampling error due to altered volatility at
different pH values, samples consisting of either water with a pH
adjusted to 8.0 or water with a pH adjusted to 3.0 and 10 ppm of
butanal, hexanal, heptanal, octanal, nonanal, decanal and
benzaldehyde were used. Carbonyl quantification revealed that there
is no significant difference in the concentration of aldehydes
between the two samples with different initial pH thus, confirming
that observed differences are true and not a sample preparation
artifact (FIG. 6).
[0225] NMR technology was also utilized to further confirm the
effect of pH in the balance of carbonyl species with increasing pH
favoring chemical species such as hemiacetals/acetals. We
successfully applied signal suppression techniques for water and
ethanol therefore increasing the signal intensity/method
sensitivity of compounds found at low concentrations. In order to
increase signal strength and be able to extract a more
comprehensive and clear image of the effect of pH the above
mentioned aldehydes were spiked in water/ethanol solutions (40/60),
at a pH 3.0 and pH 8.0 at levels of 500 ppm. The NMR spectra
resulted are shown in FIG. 7.
[0226] Results visibly show chemical shifts in the characteristic
aldehyde region (9.5-10.5 ppm) and there are noticeable intensity
differences between the two different pH samples with the lower pH
sample having significantly higher levels of aldehydes. Another
important observation was the appearance of chemical shifts in the
region between 3-5 ppm for the basic sample (pH 8.0) when compared
to the acidic (pH 3.0) sample as chemical shifts in that region are
associated with acetal-hemiacetal, lactone, lactol (cyclic
equivalent of hemiacetal), ketone, ether and ester structures.
These observations further support that pH modification and more
specifically an increase in pH value in ethanol solutions will
favor the formation of hemiacetal species and result in reduction
of aldehydes which will then affect the overall flavor profile and
the perceived smoothness and trigeminal burn of the product.
[0227] Based on the observed positive correlation between low
carbonyl species load, high pH, and improved perceived smoothness
(trigeminal sensation) we additionally exploring the sensory
effects of several food grade ingredients, which can potentially
act as effective carbonyl scavengers and thus be a feasible flavor
improvement strategy.
[0228] Sodium bisulfite was examined due to its known carbonyl
trapping ability and the fact that is a GRAS ingredient already
used in wine and beer making. Two levels of sodium bisulfite 200
and 1000 ppm (mg/L) were added to the following samples:
water/ethanol solution (60/40%), a commercially available vodka
sample (Karkov, ethanol content 40%) and a commercially available
mouthwash solution (Listerine, ethanol content 21%). The sensory
properties were examined using a degree of difference test.
Panelists were asked to evaluate the samples without and with a
nose clip in order to examine (1) the taste/trigeminal responses
alone (nose clip) and (2) taste/trigeminal with aroma (no nose
clip). When panelist used nose clips and were asked to focus on
smoothness and burning sensation both sodium bisulfite treated
samples we perceived as smoother (Table 7) supporting the efficacy
of sodium bisulfite in improving smoothness perception of vodka but
when panelist were asked to comment of the overall flavor profile
of vodka with out using nose clips it was concluded that sodium
bisulfite negatively affects the sensory properties of the products
rendering it as an impractical approach for flavor improvement.
TABLE-US-00007 TABLE 7 Average (n = 6) degree of difference ratings
for trigeminal burn of Karkov, water/ethanol solution (60/40) and
Listerine mouthwash with and without sodium bisulfite. Two
concentration of sodium bisulfite were used namely, 200 and 1000
ppm (mg/L). Sample Rating.sup.1 Water/ethanol (Blind Control)
-0.50.sup.a Water/ethanol 200 ppm SBS -2.40.sup.b Water/ethanol
1000 ppm SBS -5.70.sup.c Karkov (Blind control) 0.70.sup.a Karkov
200 ppm SBS -2.70.sup.b Karkov 1000 ppm SBS -7.40.sup.c Listerine
(Blind control) -0.50.sup.a Listerine 200 ppm SBS -3.25.sup.b
Listerine 1000 ppm SBS -7.90.sup.c .sup.1Different letters indicate
statistically significant difference determined by one-way ANOVA
analysis and Dunnetts test (.alpha. = 0.05); .sup.anot
significantly different than control. SBS: sodium bisulfite.
[0229] Anthranilites were also examined as a potential ingredient
technology for flavor improvement due to their structure reactivity
towards trapping carbonyl species. The presence of amine group,
which can act as a nucleophile, makes anthranilites good scavengers
by reacting with the electrophilic carbonyl groups and forming
adducts. Additionally anthranilites are known to have pleasant
aromas such as orange blossom and grape and are approved for use as
food flavorants. Methyl, ethyl, cinnamyl and isobutyl anthranilites
were tested and were incorporated in relatively low levels (5 ppm)
in order to maintain pleasant odor all these ingredient have
relatively potent aromas. Results from the degree of difference
test comparing treated samples (water/ethanol solutions and
commercial vodka sample) with control and utilizing a nose clips
revealed that there was no significant difference between samples
regarding smoothness and burning sensation. Results could be due to
the low levels incorporated (and low activity) in water/ethanol
solutions and vodka. Higher levels were not investigated as their
influence on the characteristic aroma profile is significant and is
likely not a feasible approach for "clean" flavor profile products.
The use of anthranilites, at higher levels and/or in as a mixture
of compounds, could be explored in the future as a feasible
treatment in different alcoholic products.
[0230] Amides were explored as potential ingredient technology due
to their structure reactivity and their nucleophilicity. Five amide
compounds (Lactamide, 2-hydroxyethyl lactamide, 2-hydroxyethyl
propionamide, N,N'-bis(2-hydroxyethyl)oxamide, and butyramide,
shown in Scheme 4) were explored as potential treatments and added
at levels of 50 mg/L. Sensory properties of amide treated
water/ethanol solution (60/40), Listerine mouthwash and Karkov
vodka were examined employing a degree of difference test and
results indicated that although smoothness-burning sensation was
overall significantly improved the astringency of the samples
increased resulting in an overall undesirable flavor profile.
Butyramide was the only exception with no perceived increase in
astringency and overall improved smoothness.
##STR00004##
[0231] Trehalose (Scheme 5) was also examined as a potential
carbonyl scavenger as well as in combination with pH modification.
Trehalose is expected to be more nucleophilic under alkaline
conditions and thus more reactive towards electrophilic carbonyls
such as aldehydes. Additionally, trehalose has a pleasant sweet
taste, is resistant to acid hydrolysis, is fairly cost effective
and already has GRAS status, thus making it a suitable choice for a
potential ingredient technology.
##STR00005##
[0232] Trehalose was added (0.2% w/w) to the following samples, a
water/ethanol (60/40) solution, Karkov vodka and E&J VS brandy
as well as the corresponding pH modified samples. The pH modified
sample of water/ethanol (60/40) solution and Karkov vodka were
adjusted to 8.0 and for E&J VS brandy to 7.0. A
degree-of-difference test was conducted in order to determine the
trigeminal burn difference between the trehalose and/or pH
modified-trehalose treated samples as compared to original samples.
Overall the addition of trehalose significantly (p<0.05) reduced
trigeminal burn perception in all tested samples (see Tables 8, 9
and 10). When trehalose addition was accompanied with pH
modification the observed reduction of trigeminal burn was
effective than just the pH modification alone.
TABLE-US-00008 TABLE 8 Average (n = 6) degree of difference ratings
for trigeminal burn of Karkov vodka with and without pH
modification or trehalose addition. Sample Rating.sup.1 Karkov -
Blind Control 1.40.sup.a* Karkov trehalose -3.40.sup.b Karkov pH
8.0 -8.00.sup.c Karkov pH 8.0 trehalose -9.40.sup.d .sup.1Different
letters indicate statistically significant difference determined by
one-way ANOVA analysis and Dunnetts test (P < 0.05); .sup.anot
significantly different than control.
TABLE-US-00009 TABLE 9 Average (n = 6) degree of difference ratings
for trigeminal burn of water/ethanol solution (60/40) with and
without pH modification or trehalose addition Sample Rating.sup.1
Water/ethanol pH 6.3 - Blind Control 0.60.sup.a* Water/ethanol pH
6.3 - trehalose -2.50.sup.b Water/ethanol pH 8.0 -5.80.sup.c
Water/ethanol pH 8.0 - trehalose -7.75.sup.d .sup.1Different
letters indicate statistically significant difference determined by
one-way ANOVA analysis and Dunnetts test (P < 0.05); .sup.anot
significantly different than control.
TABLE-US-00010 TABLE 10 Average (n = 6) degree of difference
ratings for trigeminal burn of E&J VS brandy with and without
pH modification and trehalose addition Sample Rating.sup.1 E&J
VS brandy pH 4.35 - Blind Control 0.90.sup.a* E&J VS brandy pH
7.00 -5.50.sup.b E&J VS brandy pH 7.00 - trehalose -7.00.sup.b
.sup.1Different letters indicate statistically significant
difference determined by one-way ANOVA analysis and Dunnetts test
(.alpha. = 0.05); .sup.anot significantly different than
control.
[0233] The effect of trehalose was also analytical determined by
monitoring the concentration of carbonyl species in the Karkov
samples that are presented in FIG. 8. Trehalose was found to reduce
the concentration of carbonyl species when compared to original
Karkov vodka. The treatment of trehalose in combination with pH
modification further resulted in a higher reduction of carbonyl
species and a large increase in acetal species (100-fold increase
of acetaldehyde diethyl acetal was reported). The analytical and
sensorial data were in agreement supporting that the balance
between carbonyl species and more specifically between carbonyls
and their acetal/hemiacetal species affects the perceived
trigeminal burn intensity and the development of the desirable
maturation flavor profile. Thus, in more complex distilled products
like brandy, rum and whiskey, where rich aroma and color is
expected in the final product, it is possible to modulate the
chemical balance via pH modification and addition of aldehydes like
cinnamic aldehyde and vanillin. These aldehydes in turn could yield
pleasant acetal species with sweet, spicy and fresh aroma such as
cinnamaldehyde diethyl acetal or ethyl vanillin diethyl acetal and
thus enhance maturation and smoothness by minimizing both
trigeminal ethanol burn and reduction of astringent and bitter
notes. In order to explore this concept, three samples of E&J
VS original brandy were prepared, one with added aldehydes
(cinammic aldehyde and vanillin, 1 mg/L) and two with both added
aldehydes and trehalose (0.2%) both with and without pH
modification (pH 7.00). A difference from control sensory
evaluation was used to evaluate the samples. E&J VS original
with no modification or addition was used as control (and blind
control) and the panelists were asked to focus on trigeminal
burning sensation and maturation differences between samples and
after rating to report if perceived difference was positive or
negative. The results are presented in Table 11 and indicated that
addition of aldehydes alone negatively impacted the alcohol
smoothness and maturation (more burn intensity noted) perceived by
the panelists. However when the addition of the selected aldehydes
was coupled with pH modification and trehalose addition, the
trigeminal burn intensity was reduced and maturation was improved
as reported by panelists. Overall this product had reduced
trigeminal burn and astringency and richer, slightly sweet creamier
flavor profile giving the impression of a more mature brandy when
compared to a control sample of E&J VS brandy. Sensory results
obtained by degree of difference test are shown in Table 11.
TABLE-US-00011 TABLE 11 Average (n = 6) degree of difference
ratings for trigeminal burn of E&J VS brandy with and without
pH modification and trehalose and/or select aldehyde compound
addition. Sample Rating.sup.1 E&J VS (pH 4.35) - Blind Control
0.90.sup.a* E&J VS (pH 4.35)-CNA-VNL 1.70.sup.a E&J VS pH
7.00-CNA-VNL -8.20.sup.b E&J VS pH 7.00-CNA-VNL-trehalose
-9.40.sup.b .sup.1Different letters indicate statistically
significant difference determined by one-way ANOVA analysis and
Dunnetts test (.alpha. = 0.05); .sup.anot significantly different
than control, CNA: cinnamic aldehyde. VNL: vanillin.
Example 2
Introduction
[0234] Vodka is a spirit drink produced by fermentation and
distillation of grain, potatoes, sugar beets, grapes, or cassava
(1, 2). During vodka production, the alcohol obtained from the
fermentation and distillation processes undergoes further
processing such as passing through charcoal or carbon filters (see
Ng, L. et al., J. Sci. Food Agric., 1996, 70 (3), 380-388). The
final product is obtained by blending the rectified spirit and
demineralized water, which is filtered through activated carbon and
deionization columns, followed by additional filtering before
bottling.
[0235] The standard of identity of vodka is defined in Title 27 of
the Code of Federal Regulations of Alcohol, Tobacco and Firearms
Sec. 5.22 where vodka complies with the following: [0236] (a) Class
1; neutral spirits or alcohol. "Neutral spirits" or "alcohol" are
distilled spirits produced from any material at or above
190.degree. proof, and, if bottled, bottled at not less than
80.degree. proof. [0237] (1) "Vodka" is neutral spirits so
distilled, or so treated after distillation with charcoal or other
materials, as to be without distinctive character, aroma, taste, or
color. Vodka accounts for nearly one-third of all distilled spirit
sales and the market share has been steadily increasing for the
last decade. According to the Beverage Information Group's Handbook
Advance 2012, vodka sales increased by 6% from last year. This is a
result of increased sales in the premium/ultra-premium price
segments exhibiting a shift in consumer trends towards high quality
products. The vodka market is mature, with a large number of
available products, thus the best strategy for a brand to survive
is to follow the current market trend and differentiate based on
flavor quality.
[0238] Although vodka should be a reasonably pure mixture of
alcohol and water; products typically show differences in flavor
and thus consumer appeal among brands. According to FDA, the
Alcohol and Tobacco Tax and Trade Bureau, as well as the EU
commission, vodka can contain food grade additives such as sugar,
citric acid, glycerin and food grade flavorings which of course can
greatly influence the flavor profile of the spirit.
[0239] Understanding the molecular basis of vodka flavor perception
provides opportunities for product optimization. The "ingredients"
used for fermentation and the number of distillation and filtration
steps that a product undergoes naturally determine the flavor
profile of the final product. Based on the scarce available
information, fuse oils and congeners compounds (fermentation
products i.e. ketones, aldehydes, alcohols) are consisted to affect
the overall flavor.
Phase 1
Methods
Chemical Fingerprint: Selection of High and Low Rated Products
[0240] The selection of different quality rated vodka products was
performed based on consumer rating and weighted average of scores
and awards from the International Wine and Spirit Competition, San
Francisco World Spirits Competition, Beverage Testing Institute and
Wine Enthusiast magazine (http://vodka.findthebest.com/). Twelve
products that ranged widely in consumer ratings and covered the
entire spectrum of vodka classifications (premium, super premium
and ultra premium) were selected for the initial screening (Table
12). After an initial sensory screening, six products were selected
for further investigation based on a simplify samples set and a
wide range in the flavor profile. Namely Zyr, Karkov, UV, Jean-Marc
XO, Luksosowa and Grey goose.
TABLE-US-00012 TABLE 12 Brand Country of origin Base Rating Zyr
Russia Winter wheat 96 UV USA Grain* 87 Sky 90 USA Wheat 86 Ketel
one Holland Wheat 80 Jean-Marc XO France French wheat 74 Krystal
head Canada Grain* 72 Grey goose France Wheat 71 Chopin Poland
Potato 71 Prairie Organic USA Grain* 60 Gordon's UK Grain* n/a
Luksusowa USA Potato n/a Karkov USA Grain* 19 *No available
information on the type of grain used for production.
[0241] The correlation between pH and flavor quality (as it related
to trigeminal burn and overall smoothness) of selected vodka
samples was investigated.
Materials and Methods
[0242] Measurement and Adjustments of pH
[0243] The pH of each sample was measured using a sure-flow pHe
electrode specifically designed for pH measurements in high ethanol
content solutions.
[0244] Sensory Evaluation/pH Effect
[0245] Two vodka samples, ZYR and Karkov (edges of the vodka
quality spectrum analyzed) were selected and their pH was adjusted
from 8.0 for Zyr (original) to 3.0 and from 3.0 for Karkov
(original) to 8.0 using food grade phosphoric acid and sodium
hydroxide respectively. Six panelists were selected based on
product usage and familiarity, discrimination ability and task
comprehension. The panelists have been trained with a "smoothness"
(trigeminal burn) reference scale consisting of solutions of pure
food grade ethanol: nanopure water (40:60) without and with added
glycerin at levels of 0.2, 0.5, 1 and 2% in order to familiarize
with the sensory attributes of interest (i.e. trigeminal burn).
[0246] Determination of Glycerin Concentration in Vodka Samples
[0247] Glycerol was measured according to the official method of
American Oil Chemical Society (AOCS) Ea 6-51. This method can be
used to determine polyalcohols containing three or more adjacent
hydroxyl groups (i.e glycerol). Other polyalcohol compounds do not
react at room temperature so there is extremely low possibility of
interference. The reaction mechanism is shown below:
CH.sub.2OH--CHOH--CH.sub.2OH+2NaIO.sub.4.fwdarw.HCOOH+2HCOH+2NaIO.sub.3+-
H.sub.2O
Formic acid (product) is used to quantify glycerol by base
titration. The pH of samples was adjusted to 8.1 (indicator end
point) with 0.05N sodium hydroxide solution. Blank solutions were
prepared containing 40% ethanol in nanopure water with no glycerol
as well as with 500 mg of glycerin to test the accuracy of the
method in the presence of ethanol. All experiments were performed
in duplicates. The periodate reaction occurred by adding 25 ml of
sodium periodate solution while stirring. The flasks were covered
with a watch glass and left standing for 30 minutes at room
temperature in the dark. At the end of this period of time, 5 mL of
50% ethylene glycol solution were added to each sample and allowed
to stand for another 20 minutes. The samples and the blank were
titrated with sodium hydroxide solution 0.125N, using a pH meter to
determine the end point, pH 6.5.+-.0.1 for the blank, and
8.1.+-.0.1 for the sample. The final volume used to neutralize the
sample was recorded to quantify the glycerol percentage in vodka
samples. The following equation was used to calculate the final
glycerol concentration:
Glycerol (wt %)=[(S-B).times.N.times.9.209]/W
where: S=volume in mL of sodium hydroxide solution to titrate
sample B=volume in mL of sodium hydroxide solution to titrate blank
N=normality of sodium hydroxide W=mass of sample in grams
Results and Discussion
[0248] The pH values of six vodka samples were determined and
further compared to the quality ratings (see Table 13). The direct
correlation between pH and the quality rating of these samples is
apparent. The change in the noted pH of vodka samples can occur
based on the extent of sample purification resulting in removal of
compounds (such as acids) by absorption or distillation methods.
Because of the apparent relationship between pH and flavor quality
of vodka, this parameter was further investigated. The influence of
pH on the taste profile of the two vodka samples, ZYR and Karkov
(the edges of flavor quality spectrum) was conducted by adjusting
Zyr from 8.0 to 3.0 and Karkov from 3.0 to 8.0 using food grade
phosphoric acid and sodium hydroxide, respectively. These samples
were presented to panelists to rate the overall trigeminal burn
intensity and smoothness. A standard scale for trigeminal burn and
smoothness was developed using standards consisting of 0-2%
glycerin in 40% ethanol (smoothness increased with glycerin
concentration) for sample comparison. The original Zyr sample at pH
8.0 was rated smoother than the 2% glycerin sample while Karkov was
on the opposite end of the spectrum with high trigeminal burn
(similar to 40% ethanol). When the pH of Zyr was decreased, the
smoothness rating also decreased (trigeminal burn increased), while
increasing the pH of Karkov similarly increased smoothness rating
(trigeminal burn decreased) (FIG. 9).
TABLE-US-00013 TABLE 13 pH values and quality index of select vodka
samples Vodka pH value Quality Index Zyr 8.0 90 UV 6.6 78 Grey
Goose 6.1 70 Jean-Marc XO 5.7 73 Luksusowa 5.7 75 Karkov 3.0 39
[0249] Based on an observed smoothness of ZYR that was similar in
comparison to the 2% glycerin standard ethanol solution, the levels
of glycerin were subsequently quantified in all six vodka samples.
Glycerin is a known additive to alcoholic beverages and distilled
spirits, associated with smoothness and improved "body" and flavor.
Only one of the tested vodka samples, Jean-Marc XO had added
glycerin (at 0.18%). Thus the addition of glycerin as a
flavor-modulating agent in the remaining five other vodka samples
(Table 13) such as in ZYR was eliminated.
[0250] Additionally, further exploration of the effect of pH on
trigeminal burn and smoothness is warranted, as a strategy for
flavor improvement. The equilibrium between aldehydes, alcohols,
hemiacetals and acetals in vodka and in distilled spirits is known
to be affected by pH and ethanol levels typical of these products
and over time of years (see Perry, D R 1986: Whisky Maturation
Mechanisms. In Proc. 2nd Aviemore Conf. Malt. Brew. Distilling,
(eds) Campell, I and Priest, F G. Institute of Brewing, London, pp
409-412). These products could significantly affect the overall
flavor as aldehydes have been associated with pungent, sharp aromas
while acetals are more pleasant and fruity (see Russell I., Stewart
G., Whisky: Technology, Production and Marketing 2003, Elsevier
Ltd.; and Perry, D R 1989: Odour intensities of whisky compounds.
In Distilled Beverage flavor: Recent developments. Piggot, J R and
Paterson, A. Ellis Horwood, Chichester, UK, pp 200-207) the effect
of pH on overall aroma smoothness is demonstrated and a correlation
between increased pH and increased aroma smoothness is
observed.
Phase 2
[0251] Prior results described herein demonstrated a positive
correlation between pH and the flavor quality of vodka. It is known
that the equilibrium between aldehydes, alcohols, hemiacetals and
acetals in vodka and distilled spirits are affected by pH and
ethanol levels typical of these products (see Perry, D R 1986:
Whisky Maturation Mechanisms. In Proc. 2nd Aviemore Conf. Malt.
Brew. Distilling, (eds) Campell, I and Priest, F G. Institute of
Brewing, London, pp 409-412). Consequently these products could
significantly affect the overall flavor. Aldehydes have been
associated with pungent, sharp aromas as well as bitterness and
astringency and acetals are more pleasant and fruity (4, 5). In
this phase, the focus was to characterize chemical balance between
carbonyl species and fusel oils (hemiacetals/acetals) in vodka
systems and related impact on the sensory properties and more
specifically on trigeminal burn. Carbonyl scavengers were utilized
to investigate the effect of carbonyl species on the sensory
properties of vodka. Karkov and Zyr vodkas were selected for the
method development and sensory evaluation as they represent the
edges of the flavor quality spectrum of selected vodka products
(Table 13).
Materials and Methods
Carbonyls Species Fingerprint Determination
[0252] Dynamic Headspace Analysis
[0253] An automated dynamic headspace method was developed for the
identification and quantification of aldehydes, ketones,
acetals/hemiacetals and fusel oils. Analysis was performed using a
6890 GC equipped with a 5973 Mass Selective Detector (Agilent
Technologies), Thermal Desorption Unit (TDU, Gerstel), PTV inlet
(CIS 4, Gerstel) and MPS 2 with headspace and DHS option (Gerstel).
A highly inert CP-SIL 5CB GC column, which withstands large solvent
injections, (desirable due to the high ethanol content of our
samples) was used for chromatographic separation. Method was
optimized and the analysis and dynamic headspace conditions are
reported in Tables 14 and 15 respectively.
TABLE-US-00014 TABLE 14 Column information and Inlet and GC oven
operating parameters employed for chromatographic separation of
analytes of interest. Analysis conditions PTV Tenax TA liner,
solvent vent (60 mL/min) at 0 kPa splitless (2 min), 20.degree. C.
(0.2 min); 10.degree. C./s; 300.degree. C. (5 min) Column 25 m
CP-SIL 5CB 0.15 mm .times. 2.0 .mu.m He, constant flow = 0.5 mL/min
Oven 40.degree. C. (10 min); 10.degree. C./min; 280.degree. C. (6
min) MSD Scan, 28-350 amu
TABLE-US-00015 TABLE 15 Optimized dynamic headspace (DHS) and
thermal desorption (TDU) flow and temperature profiles employed for
trapping and injecting analytes of interest. Dynamic headspace DHS
conditions Chemical Tenax TA trap DHS 30.degree. C. trap
temperature, 60.degree. C. inc temperature (10 min) 50 mL purge
volume, 10 mL/min purge flow 10 mL dry volume, 5 mL/min dry flow
TDU solvent venting 20.degree. C. (1 min); 720.degree. C./min;
110.degree. C. (1 min); 720.degree. C./min; 300.degree. C. (3
min)
[0254] Polymer-Bound Hydrazines/Carbonyl Scavengers
[0255] Si-Tosyl hydrazine (230-400 mesh) and sulfonyl hydrazine
(30-60 mesh) with a loading capacity of 0.8 mmol/g and 1.6-3 mmol/g
respectively were used. The mechanism of the trapping reaction
between the polymer hydrazines and carbonyl species is presented in
FIG. 2, along with the structure of the scavengers used. The
experimental protocol followed for sample preparation prior to
sensory analysis is illustrated in FIG. 10.
[0256] Sensory Analysis
[0257] For sensory evaluation, six panelists were selected based on
product usage and familiarity, discrimination ability and task
comprehension. The panelists have been trained with a "smoothness"
(trigeminal burn) reference scale consisting of solutions of pure
food grade ethanol: nanopure water (40:60) without and with added
glycerin at levels of 0.2, 0.5, 1 and 2% in order to familiarize
with the sensory attributes of interest (i.e. trigeminal burn).
[0258] Degree-of-difference tests were used to estimate the
difference of trigeminal burn intensity between the control samples
and treated samples (pH modified and/or hydrazine treated). A
15-point linear scale was used to indicate differences in
trigeminal burn of the samples ranging from no difference (0) to
extremely different (15). A positive and a negative scale were used
to capture both possible directional changes. A negative rating was
used when the trigeminal burn intensity decreased whereas a
positive value indicated an increase in trigeminal burn intensity.
All samples were presented with 3-digit randomized codes at room
temperature and panelists with and without nose clips during
evaluation.
[0259] .sup.1H NMR for Analysis of Alcoholic Beverages
[0260] Nuclear magnetic resonance (NMR) spectroscopy was used to
analyze the chemical fingerprint of different vodkas and the effect
of pH (after 24 hrs of adjustment) and hydrazine scavengers. NMR
sprecta collection was performed as described by Monakhova, et al.,
Magn. Reson. Chem., 2011, 49, 734-739. Code was developed and
optimized for signal suppression of both ethanol and water and a
Bruker 700 Ultrashield (5 mm TXI 700 MHz Z-Gradient). For sample
preparation the buffer used was as follows: pH=7.4 (1.5 M
monopotassium phosphate (KH.sub.2PO.sub.4) in deuterated water
D.sub.2O, 0.1% 3-(trimethylsilyl)-propionateacid-d4 (TSP), 3 mM
Sodium Azide (NaN.sub.3). Data was processed and handled using
TopSpin.
Results and Discussion
[0261] Dynamic headspace analysis of Karkov (pH 3.0) and Zyr (pH
8.0) vodka samples are shown in FIG. 11. The chromatograms obtained
from Karkov were more populated with aldehydes, ketones and acids
as well as at higher concentrations when compared to Zyr, results
shown in Table 16. The observed clear difference between Karkov (pH
3.0) and Zyr (pH 8.0) in content of carbonyl species such as
aldehydes and ketones indicated a correlation between pH and the
number/quantity of carbonyl compounds. Therefore pH could be
affecting the balance between carbonyls and
(hemi-)acetals/(hemi-)ketals and trigeminal perception and consumer
acceptability.
TABLE-US-00016 TABLE 16 Comparison of volatile compounds identified
in Zyr and Karkov. R.T.: retention time in minutes, relative ratio
based on peak areas and internal standard recovery. Relative R.T.
Karkov Zyr Ratio 14.23 acetic acid 16.45 isovaleraldehyde 16.72
1-butanol 18.48 2-butanone-3,3-dimethyl (pinacolone) 19.18 Acetal
(ethane-1,1- diethoxy) 19.75 butyraldehyde 20.89 hexanal hexanal
3.1:1 22 lactic acid 23.13 2-heptanone 2-heptanone 0.85:1 23.4
heptanal 24.41 2-methyl-3-heptanone 2-methyl-3-heptanone 3.3:1
palmitaldehyde diallyl 24.6 acetal 24.85 benzaldehyde benzaldehyde
3.5:1 25.16 6-methyl-5-hepten-2-one one 6-methyl-5-hepten-2- 2.3:1
25.55 octanal octanal 3.7:1 26.1 2-ethyl hexanol 2-ethyl hexanol
10:1 (emollient) 26.99 acetophenone 27.21 2-nonanone 27.47 nonanal
nonanal 7.7:1 28.13 benzoic acid 28.15 ethylhexyl acetate 28.88
camphor 29.22 decanal decanal 17:1 30.85 undecanal
[0262] For example compounds such as isovaleraldhyde (herbaceous
and acrid), heptanal (fatty unpleasant aroma) and undecanal (fatty,
orange-like) were only present in Karkov vodka and although octanal
(sharp, fatty, fruity), nonanal (fatty, orange-like) and decanal
(green, fruity) were found in both Zyr and Karkov samples the later
one contained significantly higher amounts (relative ratio up to
17:1).
[0263] To further evaluate the effect of carbonyl species on the
flavor profile of vodka, two polymer-bound hydrazines carbonyl
(carbonyl and ketone) scavenging systems were evaluated. The
trigeminal burn intensity of carbonyl scavenged vodka samples were
subsequently evaluated (compared to control-untreated vodka
samples). The two different resins were selected based on loading
capacity and efficiency namely, Si-tosyl hydrazine and sulfonyl
hydrazine. Following the polymer treatment, sensory evaluation was
conducted using a degree of difference test. The panelists were
asked to evaluate how different the treated samples were from the
control using a 15-point scale. The samples were evaluated with and
without nose clips. Overall the hydrazine treated Karkov samples
(Table 17) reported to have the greatest degree of difference
compared to the control. The panelists reported hydrazine treated
Karkov as having reduced trigeminal burn and smoother flavor with a
cleaner aroma profile. Likewise hydrazine treated Zyr samples were
also found to have reduced trigeminal burn, albeit the difference
from control was not as large (Table 18). Overall the two different
hydrazine resins used resulted in flavor improvement.
Sulfonyl-hydrazine had approximately double the loading capacity of
si-tosyl hydrazine and therefore it was a more efficient scavenger
of carbonyl species, which correlated with the observed sensory
results.
TABLE-US-00017 TABLE 17 Average (n = 6) degree of difference
ratings for trigeminal burn of Karkov with and without hydrazine
treatments. Two hydrazine polymers were used as carbonyl scavengers
namely, si-tosyl hydrazine and sulfonyl hydrazine. Sample
Rating.sup.1 Evaluation with nose clips Karkov (Blind Control)
0.40.sup.a Karkov Si-tosyl hydrazine -5.00.sup.b Karkov Sulfonyl
hydrazine -9.50.sup.c Evaluation without nose clips Karkov (Blind
Control) 0.50.sup.a Karkov Si-tosyl hydrazine -4.50.sup.b Karkov
Sulfonyl hydrazine -10.70.sup.c .sup.1Different letters indicate
statistically significant difference determined by one-way ANOVA
analysis and Dunnetts test (.alpha. = 0.05); .sup.anot
significantly different than control.
TABLE-US-00018 TABLE 18 Average (n = 6) degree of difference
ratings for trigeminal burn of Zyr with and without hydrazine
treatments. Two hydrazine polymers were used as carbonyl scavengers
namely, si-tosyl hydrazine and sulfonyl hydrazine. Sample
Rating.sup.1 Evaluation with nose clips Zyr (Blind Control)
-0.40.sup.a Zyr Si-tosyl hydrazine -2.00.sup.b Zyr Sulfonyl
hydrazine -3.60.sup.c Evaluation without nose clips Zyr (Blind
Control) -0.70.sup.a Zyr Si-tosyl hydrazine -2.00.sup.b Zyr
Sulfonyl hydrazine -3.40.sup.c .sup.1Different letters indicate
statistically significant difference determined by one-way ANOVA
analysis and Dunnetts test (.alpha. = 0.05); .sup.anot
significantly different than control.
[0264] Another analytical approach utilized herein to understand
vodka flavor quality was NMR technology in order to get a more
comprehensive insight into the chemical fingerprint of vodka and
how pH as well as scavengers, alter the chemical environment. This
analytical information would help identify chemical species that
impact trigeminal burn modulating activity.
[0265] NMR analysis of alcoholic beverages can be problematic due
to the presence of ethanol and water which can result in much
higher intensities of NMR signals than the compounds of interest.
The more attractive approach in order to overcome this hindrance is
the use of suppression of undesirable NMR signals during the
experiment. Preliminary experiments showed that Zyr and Karkov
vodka have distinct NMR spectra (FIGS. 12 and 13).
[0266] The region between 2.8-2.7 ppm indicates the presence of
alcohol or methyl hydrogen atoms neighboring an aldehyde/keto group
and the signal is clearly prevailing in Karkov vodka further
suggesting that presence of such carbonyl species. Signal at
3.9-3.8 ppm could be explained by the presence of hydrogen atoms
neighboring ether or hydroxyl groups, more likely CH.sub.3 hydrogen
atoms and signals at 4.3-4.0 ppm can be associated with lactone,
lactol (cyclic equivalent of hemiacetals) and acetal structures.
Peaks at 5.4 ppm likely indicate CH.sub.2 hydrogen atoms
neighboring ether group supporting the present of acetal like
molecules in Zyr vodka.
Phase 3
Introduction
[0267] Prior results described herein demonstrated a positive
correlation between increased pH and the flavor quality of vodka.
It has been demonstrated that there is a positive correlation
between low vodka pH and increased concentration of carbonyl
species that was correlated with a decreased trigeminal burn
perception and smoothness. Additionally the use of carbonyl
scavengers resulted in improved sensory properties further
supporting that carbonyl species appear to greatly influence
smoothness, burning sensation and the overall flavor profile of
vodkas. In this phase of the project the focus was to
quantitatively determine the concentration changes of carbonyl
species in vodka systems with modified pH change and how it relates
to sensory and trigeminal burn. Karkov vodka was selected for, pH
modification experiments, quantitation of carbonyl species and
examination of potential ingredient technologies as it represents
the worst-case scenario among the initial pool of samples selected
(Table 13) for this study. GC/MS and NMR technology were used to
further confirm the hypothesis that pH affects the perceived
trigeminal burn of vodka by influencing the balance of carbonyl
species present and further demonstrate causality. In addition the
quantitative data will be used for sensory re-engineering
experiments. Food grade ingredients will also be investigated as
potential carbonyl scavengers to be used for flavor
improvement.
Materials and Methods
Carbonyls Species Fingerprint and Quantification
[0268] As a concentration step and in order to optimize the
analytical method for carbonyl species quantification, sodium
bisulfite was utilized as a scavenger. Sodium bisulfite is known to
react with aldehydes and ketones and form bisulfite adducts as
shown in Scheme 1 above, adducts then precipitate and easily
isolated via filtration.
[0269] The advantage of this reaction is its reversibility shown in
Scheme 2 above. Addition of a base such as sodium bicarbonate or
sodium hydroxide results in regeneration of carbonyl species. Based
on this reaction scheme a method coupling carbonyl scavenging,
dynamic headspace and GC/MS was developed for carbonyl species
quantification. Method details can be seen in FIG. 14.
[0270] An automated dynamic headspace (DHS) method was developed
for the identification and quantification of aldehydes, ketones,
acetals/hemiacetals and fusel oils. Analysis was performed using a
6890 GC equipped with a 5973 Mass Selective Detector (Agilent
Technologies), Thermal Desorption Unit (TDU, Gerstel), PTV inlet
(CIS 4, Gerstel) and MPS 2 with headspace and DHS option (Gerstel).
A highly inert CP-SIL 5CB GC column, which withstands large solvent
injections, (desirable due to the high ethanol content of our
samples) was used for chromatographic separation.
[0271] In order to examine and confirm (as predicted) that the
observed differences on carbonyl species quantified (by headspace
analysis) between samples with different pH values were not the
result of altered volatility of the carbonyl compounds themselves
(due to pH changes) 200 ml of water with pH adjusted to either 3.00
or 8.00 was spiked with 10 ppm of butanal, hexanal, heptanal,
octanal, nonanal, decanal and benzaldehyde and carbonyls species
were quantified via Headspace GC/MS. Experimental protocol used is
shown in FIG. 15.
Sensory Analysis
[0272] For sensory evaluation, six panelists were selected based on
product usage and familiarity, discrimination ability and task
comprehension. The panelists have been trained with a "smoothness"
(trigeminal burn) reference scale consisting of solutions of pure
food grade ethanol: nanopure water (40:60) without and with added
glycerin at levels of 0.2, 0.5, 1 and 2% in order to familiarize
with the sensory attributes of interest (i.e. trigeminal burn).
[0273] Degree-of-difference tests were used to estimate the
difference of trigeminal burn intensity between the control samples
(Karkov) and treated samples (pH modified and/or carbonyl scavenger
treated). A 15-point linear scale was used to indicate differences
in trigeminal burn of the samples ranging from no difference (0) to
extremely different (15). A positive and a negative scale were used
to capture both possible directional changes. A negative rating was
used when the trigeminal burn intensity decreased whereas a
positive value indicated an increase in trigeminal burn intensity.
All samples were presented with 3-digit randomized codes at room
temperature and panelists with and without nose clips during
evaluation.
[0274] In order to further examine causality, the effect of the
carbonyl concentration on smoothness (i.e. trigeminal burn) was
also determined by evaluating samples with added carbonyl
compounds.
.sup.1H NMR for Analysis of Alcoholic Beverages
[0275] Nuclear magnetic resonance (NMR) spectroscopy was used to
analyze the chemical fingerprint of different vodkas and the effect
of pH modification on carbonyl species in Karkov. NMR sprecta
collection was performed as described by Monakhova, et al., Magn.
Reson. Chem., 2011, 49, 734-739. Code was developed and optimized
for signal suppression of both ethanol and water and a Bruker 700
Ultrashield (5 mm TXI 700 MHz Z-Gradient). For sample preparation
two buffer systems were used to accommodate the pH of vodka
samples. Buffer 1 had a pH of 7.4, consisted of 1.5 M monopotassium
phosphate (KH.sub.2PO.sub.4 in deuterated water D.sub.2O, 0.1%
3-(trimethylsilyl)-propionateacid-d4 (TSP), 3 mM Sodium Azide
(NaN.sub.3) and was utilized for sample preparation and data
collection of pH modified Karkov (pH 8.00). Buffer 2 had a pH of
2.5, consisted of 1.5 M monopotassium phosphate (KH.sub.2PO.sub.4
in deuterated water D.sub.2O, 0.1%
3-(trimethylsilyl)-propionateacid-d4 (TSP) and utilized for sample
preparation and spectra collection of original Karkov samples (pH
3.00). Data was processed and handled using TopSpin.
Carbonyl Scavenger Treatments
[0276] Sodium Bisulfite.
[0277] Sodium bisulfite was examined as a potential ingredient
treatment as it reacts with carbonyl species to form adducts (see
Schemes 1 and 2). It is a GRAS ingredient and it is commonly added
in wine and beer to prevent yeast growth. Two levels of sodium
bisulfite were utilized, namely 200 and 1000 ppm (mg/L) and sensory
properties were examined employing a degree of difference test.
Employed levels were chosen based on commonly used concentration of
sulfites in winemaking and were well within allowable limits
(100-200 ppm of SO.sub.2 in solution). Sensory properties of the
resulted samples were examined employing a degree of difference
test and evaluation was conducted after 24, 48 and 72 hrs.
[0278] Anthranilites.
[0279] This group of chemicals was explored as a potential
treatment due to structure reactivity (Scheme 3) towards trapping
carbonyl species (presence of amine group-reactive nucleophiles
known to react with carbonyl species such as aldehydes and
ketones). Methyl, ethyl, cinnamyl and isobutyl anthranilites were
tested and were incorporated in relatively low levels (5 ppm) and
sensory properties of the resulted samples were examined employing
a degree of difference test and evaluation was conducted after 24,
48 and 72 hrs.
[0280] Amides.
[0281] This class of compounds was selected as a potential
treatment due the potential trapping reactivity towards carbonyl
species as the amide group present can act a nucleophile and react
with the electrophilic carbonyl carbon of aldehydes and ketones.
The following five amide compounds were explored as potential
treatments and added at levels of 50 mg/L: Lactamide,
2-hydroxyethyl lactamide, 2-hydroxyethyl propionamide,
N,N'-bis(2-hydroxyethyl)oxamide and butyramide. Sensory properties
were examined employing a degree of difference test and evaluation
was conducted after 24, 48 and 72 hrs.
Results and Discussion
[0282] Dynamic headspace analysis of Karkov (pH 3.0) and modified
pH Karkov vodka samples (pH 8.0) revealed significant difference in
the content of carbonyl species (see, FIG. 16). The chromatograms
obtained from the original Karkov vodka (pH 3.0) revealed more
aldehyde species and increased concentrations when compared to pH
modified Karkov (pH 8.0). Increased pH resulted in significant
reduction of aldehydes such as butanal, pentanal, hexanal,
heptanal, octanal, nonanal, decanal and benzaldehyde. The observed
difference between Karkov (pH 3.0) and modified Karkov (pH 8.0) in
content of carbonyl species was in some cases (ie. butanal,
hexanal, benzaldehyde) upwards of a 80% decrease indicating a
correlation between concentration of carbonyl species in distilled
spirits, trigeminal burn and consumer acceptability.
[0283] In order to confirm that the observed differences in the
carbonyl load between the two vodka products is not the result of
altered volatility (of the carbonyl compounds themselves) due to pH
differences two samples consisting of either water with a pH
adjusted to 8.0 or water with a pH adjusted to 3.0 and 10 ppm of
butanal, hexanal, heptanal, octanal, nonanal, decanal and
benzaldehyde were used. The same sample preparation and analytical
method as described above was used for carbonyl quantification and
results (FIG. 17) revealed that there is no significant difference
in the concentration of aldehydes between the two samples with
different initial pH.
[0284] NMR technology was also used to further confirm the effect
of pH on the balance of carbonyl species and that with increasing
pH chemical species such as (hemi-)acetals were favored. In order
to increase signal strength and be able to extract a more
comprehensive and clear image of the effect of pH the above
mentioned-quantified aldehydes were spiked in Karkov (pH 3.0) and
pH modified Karkov (pH 8.0) at 500 mg/L. The NMR spectra resulted
are shown in FIG. 18. Results visibly show chemical shifts in the
characteristic aldehyde region (9.5-10.5 ppm) and there are
noticeable intensity differences between the two different pH
Karkov samples with the lower pH vodka sample having significantly
higher levels of aldehydes. Another significant observation was the
appearance of chemical shifts in the region between 3-5 ppm for the
pH modified Karkov (pH 8.0) when compared to original Karkov (pH
3.0) as chemical shifts in that region are associated with
acetal-hemiacetal, lactone, lactol (cyclic equivalent of
hemiacetal), ketone, ether and ester structures. These observations
further support that pH modification, and more specifically an
increase, favor the formation of hemiacetal species and result in
reduction of aldehydes affect the overall flavor profile of
vodka.
[0285] Quantification of carbonyl species of the two different pH
Karkov samples that were additionally treated with sulfonyl
hydrazine resin (carbonyl scavenger) was performed and also
compared to samples with no sulfonyl hydrazine treatment; the
results are shown in FIG. 19. It seems that the sulfonyl hydrazine
scavenger was more effective in trapping carbonyls at pH 3.0 but
that could simply be a concentration effect, as initial load of
carbonyls at pH 8.0 is significantly lower. Optimization of the
scavenger treatment by implementing a solid phase extraction
cartridge could result in more conclusive information.
[0286] Sensory evaluation of pH modified and hydrazine treated
vodka samples was conducted in order to further confirm the
correlation between reduced levels of aldehydes and reduced
trigeminal burn and overall improved smoothness perception.
Panelists were asked to rank the samples based on increasing
smoothness (lower trigeminal burn) and the following order was
revealed (lowest smoothness on left, highest smoothness on right):
Karkov pH 3.0<Karkov pH 3.0 SH<Karkov pH 8.0<Karkov pH 8.0
SH. These findings further supported the negative effect of higher
quantities of aldehydes on smoothness and increasing the trigeminal
burn perception of vodka.
[0287] It has been demonstrated that increasing pH affects the
balance of carbonyl species in vodka and that correlated with
smoothness. In order to confirm that increased amounts of aldehydes
in these samples negatively affect smoothness perception and
increase burn intensity, samples were prepared with higher levels
of aldehydes (added 5 mg/L each) and immediately the panelists were
asked to rank them based on increasing smoothness: Karkov (pH 3.0),
modified Karkov (pH 8.0), original Karkov (pH 3.0)+5 ppm aldehydes
and modified Karkov (pH 8.0)+5 ppm aldehydes. During sensory
evaluation nose clips were used as to avoid the contribution of
aroma in smoothness perception and to establish the trigeminal
effect of aldehydes in alcohol perception. Panelists placed the
samples in the following order of increasing smoothness (lowest was
on the left to highest on the right): Karkov (pH 3.0)+5 ppm
aldehydes<Karkov (pH 8.0)+5 ppm aldehydes <Karkov (pH
3.0)<Karkov (pH 8.0). These results further demonstrate that
increased concentration of aldehydes are highly influential to the
flavor profile of aqueous/ethanol products, making them an
important target for flavor improvement technologies. After
approximately 48 hrs panelists were asked to evaluate the samples
again and this time the modified Karkov (pH 8.0)+5 ppm was
perceived as smoother than original Karkov (pH 3.0) demonstrating
again pH adjustment is a novel effective strategy to rapidly modify
alcohol, trigeminal sensation and maturation flavor development.
The pH effects on the concentration of carbonyl species in ethanol
solutions were noted to be time dependent and typically within a
few hours quantitative changes in the carbonyl concentrations were
observed.
[0288] Based on these results, food grade ingredients, which can
potentially act as effective carbonyl scavengers and thus be a
feasible flavor improvement strategy, were explored.
[0289] Sodium bisulfite was examined due to its known carbonyl
trapping ability and the fact that is a GRAS ingredient already
used in wine and beer making. Two levels of sodium bisulfite were
added in Karkov vodka, namely 200 and 1000 ppm (mg/L) and sensory
properties were examined employing a degree of difference test.
When panelists used nose clips and were asked to focus on
smoothness and burning sensation both sodium bisulfite treated
samples were perceived as smoother (Table 19) supporting the
efficacy of sodium bisulfite in improving smoothness perception of
vodka but when panelist were asked to comment of the overall flavor
profile of vodka without using nose clips it was concluded that
sodium bisulfite negatively affects the sensory properties of the
product and as vodka has a very characteristic flavor profile and
relatively "clean" sodium bisulfite was detectable at both levels;
however, application may still possible and may work with flavored
products.
TABLE-US-00019 TABLE 19 Average (n = 6) degree of difference
ratings for trigeminal burn of Karkov, with and without sodium
bisulfite. Two concentration of sodium bisulfite were used namely,
200 and 1000 ppm (mg/L). Sample Rating.sup.1 Karkov (Blind Control)
0.70.sup.a Karkov 200 ppm SBS -2.70.sup.b Karkov 1000 ppm SBS
-7.40.sup.c .sup.1Different letters indicate statistically
significant difference determined by one-way ANOVA analysis and
Dunnetts test (.alpha. = 0.05); .sup.anot significantly different
than control. SBS: sodium bisulfite.
[0290] Anthranilites were also examined as a potential ingredient
technology for flavor improvement due to their structure reactivity
(Scheme 3) towards trapping carbonyl species. The presence of amine
group, which can act as a nucleophile, makes anthranilites good
scavengers by reacting with the electrophilic carbonyl groups and
forming adducts. Additionally anthranilites are known to have
pleasant aromas such as orange blossom and grape and are approved
for use as food flavorants. Methyl, ethyl, cinnamyl and isobutyl
anthranilites were tested and were incorporated in relatively low
levels (5 ppm) in order to maintain pleasant odor all these
ingredient have relatively potent aromas. Results from the degree
of difference test comparing treated samples with control and
utilizing a nose clips revealed that there was no significant
difference between samples regarding smoothness and burning
sensation. Results could be due to the low levels, low activity and
insufficient time tested in vodka. Higher levels were not
investigated as their influence on the characteristic aroma profile
is significant and is likely not a feasible approach. The use of
anthranilites, at higher levels and/or in as a mixture of
compounds, could be explored as a feasible treatment in flavored
vodka products.
[0291] Amides were explored as potential ingredient technology due
to their structure reactivity and their nucleophilicity. Five amide
compounds (Lactamide, 2-hydroxyethyl lactamide, 2-hydroxyethyl
propionamide, N,N'-bis(2-hydroxyethyl)oxamide, and butyramide,
shown in Scheme 4) were explored as potential treatments and added
at levels of 50 mg/L. Sensory properties of amide treated
water/ethanol solution (60/40), Listerine mouthwash and Karkov
vodka were examined employing a degree of difference test and
results indicated that although smoothness-burning sensation was
overall significantly improved the astringency of the samples
increased resulting in an overall undesirable flavor profile.
Butyramide was the only exception with no perceived increase in
astringency and overall improved smoothness.
[0292] As described herein sensory re-engineering experiments will
be conducted using vodka model systems aiming to identify positive
and negative contributing components and determine the effect of
individual aldehydes in the overall flavor profile of vodka
products.
Phase 4
Introduction
[0293] In this phase of the project, optimization of the analytical
methodologies was performed in order to facilitate the examination
of the carbonyl fingerprint direct from vodka samples and other
relevant chemical species. Alternative food grade ingredient
technologies with trigeminal burn and smoothness modulating
activity in combination with pH modification treatments were
explored. This phase involved re-engineering experiments in order
to determine the sensory effect of individual carbonyl species
providing an understanding on how to design targeted ingredient
technologies for flavor improvement tailored to different
products.
Materials and Methods
Carbonyls Species Quantification
[0294] In order to eliminate previously employed laborious sample
preparation protocol for the quantification of chemical species of
interest an optimized automated dynamic headspace (DHS) method was
developed and employed. Analysis was performed using a 6890 GC
equipped with a 5973 Mass Selective Detector (Agilent
Technologies), Thermal Desorption Unit (TDU, Gerstel), PTV inlet
(CIS 4, Gerstel) and MPS 2 with headspace and DHS option (Gerstel).
A highly inert CP-SIL 5CB GC column, which withstands large solvent
injections (desirable due to the high ethanol content of the
samples), was used for chromatographic separation.
[0295] Analysis, dynamic headspace (DHS) conditions and MS SIM
parameters are reported in Tables 20, 21 and 22. No sample
preparation was necessary prior to analysis. Briefly, 1 mL of
sample was place in a 20 mL headspace vial and diluted with
nanopure water to final volume of 10 mL. Methyl hexanoate was added
as an internal standard (10 .mu.g).
TABLE-US-00020 TABLE 20 Column information and Inlet and GC oven
operating parameters employed for chromatographic separation of
analytes of interest. Analysis conditions PTV Tenax TA liner,
solvent vent (30 mL/min) at 0 kPa splitless (0.5 min), 20.degree.
C. (0.5 min); 10.degree. C./s; 300.degree. C. (5 min) Column 25 m
CP-SIL 5CB 0.15 mm .times. 2.0 .mu.m He, constant flow = 0.5 mL/min
Oven 40.degree. C. (10 min); 10.degree. C./min; 280.degree. C. (5
min) MSD SIM
TABLE-US-00021 TABLE 21 Optimized dynamic headspace (DHS) and
thermal desorption (TDU) flow and temperature profiles employed for
trapping and injecting analytes of interest. Dynamic headspace DHS
conditions Chemical Tenax TA trap DHS 30.degree. C. trap
temperature, 55.degree. C. incubation temp (12 min) 2000 mL purge
volume, 16 mL/min purge flow 30 mL dry volume, 7 mL/min dry flow
TDU solvent venting 20.degree. C. (0.80 min); 720.degree. C./min;
110.degree. C. (1 min); 720.degree. C./min; 300.degree. C. (4
min)
TABLE-US-00022 TABLE 22 MS/single ion monitoring parameters
employed for quantification of chemical species of interest.
Compound m/z ions Acetal 45, 73, 103 Hexanal 56, 72, 82 2-heptanone
58, 71, 114 Heptanal 55, 96, 114 Methyl 74, 87, 99 hexanoate
Benzaldehyde 77, 105, 106 Octanal 57, 69, 84 Nonanal 57, 70, 98
Decanal 57, 95, 112
Sensory Analysis
[0296] For sensory evaluation, six panelists were selected based on
product usage and familiarity, discrimination ability and task
comprehension. The panelists have been trained with a "smoothness"
(trigeminal burn) reference scale consisting of solutions of pure
food grade ethanol: nanopure water (40:60) without and with added
glycerin at levels of 0.2, 0.5, 1 and 2% in order to familiarize
with the sensory attributes of interest (i.e. trigeminal burn).
[0297] Degree-of-difference tests were used to estimate the
difference of trigeminal burn intensity between the control samples
(Karkov) and treated samples (pH modified and/or carbonyl scavenger
treated). A 15-point linear scale was used to indicate differences
in trigeminal burn of the samples ranging from no difference (0) to
extremely different (15). A positive and a negative scale were used
to capture both possible directional changes. A negative rating was
used when the trigeminal burn intensity decreased whereas a
positive value indicated an increase in trigeminal burn intensity.
All samples were presented with 3-digit randomized codes at room
temperature and panelists with and without nose clips during
evaluation.
pH Modulating Agents
[0298] To investigate the sensorial effect of different pH
modifiers, food grade sodium bicarbonate and sodium carbonate was
examined and compared to food grade sodium hydroxide, which has
been used thus far. Sodium carbonate, sodium bicarbonate and sodium
hydroxide were incorporated in samples to achieve a pH of
8.00.+-.0.05, 7.65.+-.0.05 and 8.00.+-.0.05 respectively. Sensory
properties of the pH-modified samples and the effect of pH
modifiers on trigeminal burn were examined employing a degree of
difference test. The effect of the different pH modifiers on the
levels of carbonyl species was also determined using the
above-mentioned dynamic headspace GC/MS-SIM method.
Carbonyl Scavenger Treatments
[0299] Trehalose, a food grade naturally occurring disaccharide was
employed based on its hypothesized reactivity towards carbonyls
species at elevated pH values. Trehalose was incorporated in
relatively low levels (0.2%) and sensory properties of the resulted
samples were examined employing a degree-of-difference test. The
effect of trehalose on the levels of carbonyl species was also
determined using the above-mentioned dynamic headspace GC/MS-SIM
method.
Results and Discussion
[0300] To investigate the sensorial effect of different pH
modifiers, food grade sodium bicarbonate and sodium carbonate was
compared to food grade sodium hydroxide. Panelists were asked to
compare each pH-modified sample to a control (Karkov pH 3.0) and
rate trigeminal burn and smoothness. The results revealed that all
three pH modifiers had very similar effect on trigeminal burn
reduction, but overall sodium carbonate generated a "cleaner"
smoother product. Sensory results are shown in Table 23.
TABLE-US-00023 TABLE 23 Average (n = 6) degree of difference
ratings for trigeminal burn of Karkov vodka samples treated with
sodium dicarbonate (SB, pH 7.65), sodium carbonate (SC, pH 8.0) and
sodium hydroxide (SH, pH 8.0) as compare to control (Karkov vodka
pH 3.0). Sample Rating.sup.1 Karkov (Blind control) 0.30.sup.a
Karkov SB (pH 7.65) -7.10.sup.b Karkov SC (pH 8.0) -8.40.sup.c
Karkov SH (pH 8.0) -9.30.sup.d .sup.1Different letters indicate
statistically significant difference determined by one-way ANOVA
analysis and Dunnetts test (.alpha. = 0.05); .sup.anot
significantly different than control.
[0301] The effect of sodium carbonate on the levels of carbonyl
species as compared to sodium hydroxide and the original Karkov was
also examined and the results are presented in FIG. 20. Both pH
modifiers resulted in significantly lower levels of carbonyls when
compared to the original Karkov vodka, a reduction between 30-70%
for each compound was observed for the quantified aldehydes.
Additionally the pH modifiers significantly increased the levels of
acetal species further confirming the shift of the chemical balance
towards the formation of acetal and hemi-acetal species.
[0302] Trehalose (Scheme 5) was also examined as a potential
carbonyl scavenger when in combination with pH modifiers. Trehalose
was expected to be more nucleophilic under alkaline conditions and
thus more reactive towards electrophilic carbonyls such as
aldehydes. Additionally trehalose is fairly cost effective and
already has GRAS status thus making it a suitable choice for a
potential ingredient technology. Trehalose was added (0.2% w/w) to
Karkov vodka (pH 3.0) and pH modified Karkov vodka (pH 8.0). A
degree-of-difference test was conducted in order to determine the
trigeminal burn difference between trehalose and pH
modified-trehalose treated samples as compared to original samples.
Results (Table 24) demonstrate that the addition of trehalose
significantly (p<0.05) reduced trigeminal burn perception in all
tested samples. When trehalose addition was accompanied with pH
modification the observed reduction of trigeminal burn was more
pronounced suggesting higher trapping carbonyl reactivity under
alkaline conditions.
[0303] Following the positive sensory results, the effect of
trehalose on the concentration of carbonyl species was also
examined and the results are presented in FIG. 21. Trehalose was
found to reduce the concentration of carbonyl species when compared
to original Karkov vodka. In addition, trehalose in combination
with pH modification resulted in higher reduction of carbonyl
species accompanied with a significant increase in acetal species
(100-fold increase of acetaldehyde diethyl acetal). The analytical
and sensorial data were in agreement supporting that the balance
between carbonyl species and more specifically between carbonyls
and their acetal/hemiacetal species affects the perceived
trigeminal burn intensity and maturation with acetals having a
positive impact.
TABLE-US-00024 TABLE 24 Average (n = 6) degree of difference
ratings for trigeminal burn of Karkov vodka with and without pH
modification or trehalose addition. Sample Rating.sup.1 Karkov -
Blind Control 1.40.sup.a* Karkov trehalose -3.40.sup.b Karkov pH
8.0 -8.00.sup.c Karkov pH 8.0 trehalose -9.40.sup.d .sup.1Different
letters indicate statistically significant difference determined by
one-way ANOVA analysis and Dunnetts test (P < 0.05); .sup.anot
significantly different than control.
The results described herein support the importance of the balance
between carbonyl and hemiacetal and acetal species in smoothness
perception and the feasibility of pH adjustment and ingredient
technologies as improvement strategies.
Example 3
Sensory Recombination Study
[0304] A trained sensory panel consisting of 10 judges (ages 22 to
35) evaluated the trigeminal burn intensity of 60% water 40%
ethanol solution, and a recombination model with added carbonyl
species at levels quantified in 60% water 40% ethanol solutions
when pH was adjusted at 3.0. Panelists were trained to recognize
and focus on trigeminal burn and were asked to evaluate samples
using a 10-point scale. Nanopure water and a Water/Ethanol (60/40)
solution with high levels of added aldehydes (2 ppm) represented
the edges of the reference scale namely, zero and ten,
respectively. Samples were presented in a randomized order in
three-digit coded cups and panelists were asked to rate each sample
using the 10-point reference scale.
[0305] The trigeminal burn intensity of each individual carbonyl
compound when added in a Water/Ethanol (60/40) solution was also
evaluated at the corresponding concentration following the above
mentioned sensory evaluation method. Added levels of each carbonyl
compound are presented in Table 25.
TABLE-US-00025 TABLE 25 Concentration of carbonyls species added in
Water/Ethanol (60/40) solution for the construction of
recombination models. Concentration presented in parts per million
(ppm) or mg/L. Compound Concentration (ppm) Hexanal 0.48 Heptanal
0.50 Octanal 0.05 Nonanal 1.38 Decanal 2.11 Benzaldehyde 0.67
2-heptanone 1.32
Result and Discussion
[0306] A more extensive recombination experiment was conducted to
further confirm the sensory activity of carbonyl species and
causality in trigeminal burn perception in alcohol containing
products at their native levels. Both the contribution of
individual carbonyl compounds as well as their combination on
trigeminal burn was evaluated.
[0307] The contribution of the carbonyl mixture can further confirm
causality regarding trigeminal burn perception and individual
contribution can provide information on which components can exert
the highest modulation on trigeminal burn both positive and
negative. This approach can further lead to selection of control
points for flavor improvement strategies as well as screening
strategies for selection of raw materials (i.e. alcohol
distillates) for production of alcohol containing products.
[0308] Sensory results (Table 26) revealed that the recombination
model with water/ethanol and the added mixture of carbonyl
compounds had a significantly higher trigeminal burn when compared
to a water/ethanol solution with no carbonyls added. Thus,
confirming causality of carbonyl species on trigeminal burn at
their native levels and same pH systems.
TABLE-US-00026 TABLE 26 Average (n = 10) trigeminal burn rating of
water/ethanol solution (60/40) with and without mixture of
carbonyls compounds. Carbonyl compounds were added in levels
quantified when pH of solution was adjusted to 3.0 (see Table 25).
Sample Rating Water/ethanol 6.00.sup.a Water/ethanol + carbonyls
8.62.sup.b .sup.1Different letters indicate statistically
significant difference determined by one-way ANOVA analysis and
Dunnetts test (P < 0.05)
When the contribution of individual carbonyl compounds on
trigeminal burn at their native levels was evaluated results showed
that all recombination models were rated higher than the
Water/ethanol solution (6.0) (see Table 27). Though not all
carbonyls were found to be significantly different than the control
(i.e. hexanal, heptanal and decanal) an increasing trend was
observed. The obtained information additionally facilitated the
identification of the stronger causative agents regarding
trigeminal burn intensity. Comparing added levels and intensity
rating it becomes evident that octanal is a very potent trigeminal
burn contributor as it elicited one of the highest ratings (7.13)
at only 0.05 ppm (or 0.05 mg/L). Benzaldehyde also seemed to be a
strong contributor followed by nonanal and 2-heptanone which had
the highest intensity rating. Results further support the effect of
carbonyl species on trigeminal burn perception and the selection of
carbonyl species as chemical targets for the development of
smoothness improvement strategies for alcohol containing
products.
TABLE-US-00027 TABLE 27 Average (n = 10) trigeminal burn intensity
rating of water/ethanol solution (60/40) with added carbonyl
compounds. Individual carbonyl compounds were added in levels
quantified when pH of solution was adjusted to 3.0 (see Table 25).
Recombination sample Rating Water/ethanol 6.00.sup.a Water/ethanol
+ hexanal 6.75.sup.a Water/ethanol + heptanal 6.25.sup.a
Water/ethanol + octanal 7.13.sup.b Water/ethanol + nonanal
7.31.sup.b Water/ethanol + decanal 6.56.sup.a Water/ethanol +
bezaldehyde 7.13.sup.b Water/ethanol + 2-heptanone 7.56.sup.b
.sup.1Different letters indicate statistically significant
difference determined by one-way ANOVA analysis and Dunnetts test
(P < 0.05).
Example 4
[0309] Using methods described herein (see, e.g., Examples 1-3),
the pH-modified treatment (raised to 6, 7 and 8) was further
demonstrated on select distilled spirits such as rum (Trader Vic's,
US Distilled Products Co. Princeton, M N), tequila (Cabrito, US
Distilled Products Co. Princeton, Minn.), and whiskey (Early Times,
Brown-Forman Co., Louisville, Ky.). Sensory evaluation of these
pH-modified samples confirmed there was a significant reduction of
the perceived trigeminal burn intensity and a noted smoothness
improvement in direct comparison to the unmodified samples.
[0310] All publications, patents, and patent documents are
incorporated by reference herein, as though individually
incorporated by reference. The invention has been described with
reference to various specific and preferred embodiments and
techniques. However, it should be understood that many variations
and modifications may be made while remaining within the spirit and
scope of the invention.
* * * * *
References