U.S. patent application number 13/626506 was filed with the patent office on 2014-03-27 for biogenic amine oxidizer or unreactive absorber.
This patent application is currently assigned to Multisorb Technologies, Inc.. The applicant listed for this patent is MULTISORB TECHNOLOGIES, INC.. Invention is credited to George E. McKedy.
Application Number | 20140087034 13/626506 |
Document ID | / |
Family ID | 50339098 |
Filed Date | 2014-03-27 |
United States Patent
Application |
20140087034 |
Kind Code |
A1 |
McKedy; George E. |
March 27, 2014 |
BIOGENIC AMINE OXIDIZER OR UNREACTIVE ABSORBER
Abstract
The invention relates to a package for protein containing foods
comprising a sealable food covering and, in the interior of the
covering, a permeable container wherein an oxidizer is in the
permeable container oxidizer substantially irreversibly reacts with
biogenic amines within the covering to form compounds without
objectionable odor or toxicity; in another embodiment the invention
provides a package for protein containing foods comprising a
sealable food covering and, in the interior of the covering, a
permeable container wherein an unreactive absorbent is in the
permeable container and the unreactive absorbent absorbs, but does
not react with biogenic amines within the covering to largely
remove the biogenic amines from the package.
Inventors: |
McKedy; George E.;
(Williamsville, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MULTISORB TECHNOLOGIES, INC. |
Buffalo |
NY |
US |
|
|
Assignee: |
Multisorb Technologies,
Inc.
Buffalo
NY
|
Family ID: |
50339098 |
Appl. No.: |
13/626506 |
Filed: |
September 25, 2012 |
Current U.S.
Class: |
426/124 ;
206/204; 426/129 |
Current CPC
Class: |
B65D 81/268 20130101;
B65D 81/2084 20130101 |
Class at
Publication: |
426/124 ;
426/129; 206/204 |
International
Class: |
B65D 81/26 20060101
B65D081/26; B65D 81/20 20060101 B65D081/20 |
Claims
1. A package for protein containing foods comprising a sealable
food covering and, in the interior of the covering, a permeable
container wherein an oxidizer is in the permeable container
oxidizer substantially irreversibly reacts with biogenic amines
within the covering to form compounds without objectionable odor or
toxicity.
2. The package of claim 1 wherein the biogenic amine in the
covering consists of at least one member selected from the group of
trimethylamine, tyramine, tryptamine, phenylamine, histamine,
tryptamine, phenylamine, putrescine, phenylethylamine, agmatine,
spermidine, spermine, and cadaverine.
3. The package of claim 1 wherein the oxidizer comprises hydrogen
peroxide or sodium chlorite.
4. The package of claim 1 wherein the oxidizer present is
sufficient to reduce biogenic amines to less than 10 ppb when a
closely wrapped 4 ounce piece of fish is stored at 40.degree. for
seven days.
5. The package of claim 1 wherein the oxidizer is sufficient to
reduce biogenic amines to less than 5 ppb when a closely wrapped 4
ounce piece of fish is stored at 40.degree. for seven days.
6. The package of claim 1 wherein the oxidizer is absorbed onto a
carrier consisting of at least one of activated carbon, silica gel,
clay and molecular sieve.
7. The package of claim 1 wherein the permeable container is a gas
permeable but water impermeable container.
8. The package of claim 7 wherein the permeable container is a
sachet.
9. The package of claim 1 wherein the oxidizer is absorbed onto a
carrier.
10. The package of claim 1 wherein the permeable container is
adhered to the inside of the food covering.
11. A food package comprising a sealed food covering, a protein
containing food in the covering, and a permeable container in the
covering, wherein an oxidizer is in the permeable container and the
oxidizer substantially irreversibly reacts with biogenic amines to
form compounds without objectionable odor or toxicity.
12. The package of claim 11 wherein the biogenic amine in the
covering consists of at least one member selected from the group of
trimethylamine, tyramine, tryptamine, phenylamine, histamine,
tryptamine, phenylamine, putrescine, phenylethylamine, agmatine,
spermidine, spermine, and cadaverine.
13. The package of claim 11 wherein the oxidizer comprises hydrogen
peroxide or sodium chlorite.
14. The package of claim 11 wherein the oxidizer is sufficient to
reduce biogenic amines to less than 10 ppb when a 4 ounce piece of
fish is stored at 40.degree. for seven days.
15. The package of claim 13 wherein the oxidizer is absorbed onto a
carrier consisting of at least one of activated carbon, silica gel,
clay and molecular sieve.
16. The Package of claim 11 wherein the permeable container is gas
permeable but water impermeable container.
17. The package of claim 16 wherein the permeable container is a
sachet.
18. The package of claim 11 wherein the permeable container is
adhered to the inside of the food covering.
19. A package for protein containing foods comprising a sealable
food covering and, in the interior of the covering, a permeable
container wherein an unreactive absorbent is in the permeable
container and the unreactive absorbent absorbs, but does not react
with biogenic amines within the covering to largely remove the
biogenic amines from the package.
20. The package of claim 19 wherein the biogenic amine in the
covering consists of at least one member selected from the group of
trimethylamine, tyramine, tryptamine, phenylamine, histamine,
tryptamine, phenylamine, putrescine, phenylethylamine, agmatine,
spermidine, spermine, and cadaverine.
21. The package of claim 1 wherein the unreactive absorbent
comprises activated carbon or molecular sieve.
22. The package of claim 19 wherein the unreactive absorbent is
sufficient to reduce biogenic amines to less than 5 ppb when a
closely wrapped 4 ounce piece of fish is stored at 40.degree. for
seven days.
23. The package of claim 19 wherein the permeable container is a
gas permeable but water impermeable container.
24. The package of claim 7 wherein the permeable container is a
sachet.
25. The package of claim 19 wherein the permeable container is
adhered to the inside of the food covering.
26. A food package comprising a sealed food covering, a protein
containing food in the covering, and a permeable container in the
covering, wherein an unreactive absorbent is in the permeable
container and the unreactive absorber absorbs, but does not react
with biogenic amines to largely remove biogenic amines from the
package.
27. The package of claim 19 wherein the biogenic amine in the
covering consists of at least one member selected from the group of
trimethylamine, tyramine, tryptamine, phenylamine, histamine,
tryptamine, phenylamine, putrescine, phenylethylamine, agmatine,
spermidine, spermine, and cadaverine.
28. The package of claim 19 wherein the unreactive absorbent
comprises activated carbon or molecular sieve.
29. The package of claim 19 wherein the oxidizer is sufficient to
reduce biogenic amines to less than 10 ppb when a 4 ounce piece of
fish is stored at 40.degree. for seven days.
30. The Package of claim 19 wherein the permeable container is gas
permeable but water impermeable container.
31. The package of claim 30 wherein the permeable container is a
sachet.
32. The package of claim 19 wherein the permeable container is
adhered to the inside of the food covering.
Description
FIELD OF THE INVENTION
[0001] This invention relates to the removal of biogenic amines
during food storage and packaging.
BACKGROUND OF THE INVENTION
[0002] One of the challenges food packaging industry has to cope
with is to preserve packaged goods as long as possible, in order to
increase the shelf life of the package. A particular problem is
encountered in modified atmosphere packagings (MAP): these
packagings present a headspace between the packaged good and the
packaging film covering the packaged goods, where some unwanted
compounds may accumulate during the shelf life. It is known to add
additives and substances to packaging films in order to either
release substances to the packaged good or to remove substances,
either present in the headspace of the packages or generated by the
packaged good, from the headspace.
[0003] These so-called active packaging products are for instance
capable of removing oxygen, sulfites or aldehydes, from the
packaging headspace. U.S. Pat. No. 5,654,061 to Visioli,
incorporated herein by reference for all purposes, discloses the
incorporation of zeolites into the packaging seal layer in order to
adsorb volatile odorous sulfur compounds from the packaging
headspace and therefore improve the consumer acceptance of packaged
poultry.
[0004] Until recently, fresh fish has been normally transported on
ice and then distributed and sold as quickly as possible. Only
recently has the packaging of fish in modified atmosphere started.
Nevertheless, due to the problem of generation of amines during
storage of fish, the packaging of fresh fish is still not common.
Although amines generated by bacteria during the aging of fish can
be considered as a freshness indicator, they usually smell bad and
their accumulation in the headspace of fresh fish packages can lead
to rejection by the consumer despite the fact that the fish can
still be considered as fresh. In consequence, although the shelf
life of fresh fish packaged in MAP can be more than doubled, and
more cost effective distribution channels can be used, fresh fish
packaging has not yet had the success one could have expected.
Removing some of these amines would significantly reduce the number
of rejects and extend the shelf life without compromising consumer
safety and health.
[0005] Most of the solutions to this problem provided in the art
have in common that they require either the addition of a polymer
or substance to the package or the incorporation of an additional
component into one of the layers of the multilayer film of the
flexible film that makes up the package. JP 59-162832 A2 claims the
addition of a polymeric substance, e.g. polyacrylate, to a
vegetable package to remove bad odor such as amines from the
package.
[0006] US 2002/010-6466-Hausmann at Al discloses the formation of a
polymer film comprising up copolymer of ethylene with carboxylic
acid to absorb odiferous compounds when packaging materials such as
fish.
[0007] Mohan et al. in Food Research International 42 (2009)
411-416 discusses biogenic amine formation in seer fish and the use
of oxygen absorbers comprising iron and citric acid in combination
with chilling to reduce the amines.
[0008] U.S. Pat. No. 5,654,061-Visioli discloses sulfide scavenging
packaging materials.
[0009] There is still a need for a package useful for packaging
fish or other perishable food items that would remove volatile
odiferous compounds, and particularly amines, from inside of the
package.
PROBLEM TO BE SOLVED BY THE INVENTION
[0010] There's a need for packaging that will absorb biogenic
amines given off by protein such as fish and meat that is packaged
for sale. Absorption of these materials will prolong the shelf life
of the product.
BRIEF SUMMARY OF THE INVENTION
[0011] The invention provides a package for protein containing
foods comprising a sealable food covering and, in the interior of
the covering, a permeable container wherein an oxidizer is in the
permeable container oxidizer substantially irreversibly reacts with
biogenic amines within the covering to form compounds without
objectionable odor or toxicity.
[0012] In another embodiment the invention provides a package for
protein containing foods comprising a sealable food covering and,
in the interior of the covering, a permeable container wherein an
unreactive absorbent is in the permeable container and the
unreactive absorbent absorbs, but does not react with biogenic
amines within the covering to largely remove the biogenic amines
from the package.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is cross-sectional schematic view of a label or patch
with absorbent of the invention.
[0014] FIG. 2 is a cross-sectional schematic of a sachet containing
the biogenic amines absorber of the invention.
[0015] FIG. 3 is a schematic view of an invention package utilizing
the biogenic amines absorber in a label.
[0016] FIG. 4 is a schematic cross-sectional view of the use of a
biogenic amine absorber sachet in package.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The invention has numerous advantages over the prior art.
The invention provides a method of increasing the shelf life of
protein rich foods such as meat and fish at low-cost while
generally using present packaging and techniques. Materials of the
invention are safe and prevent the formation of toxins in stored
meat and fish. The materials of the invention have the advantage
that they may be presented in the food packaging art in a way that
is familiar to the art and readily carried out in protein
packaging. The invention increases the safety of stored foods while
preserving their taste. These and other advantages will be apparent
from the drawings and detailed description below.
[0018] FIG. 1 is a schematic illustration of an absorber patch or
label for biogenic amines. The patch would be adhered to the inside
of a covering forming a food package. The patch 10 is comprised of
a removable base 12 of a strippable material that will not adhere
significantly to adhesive layer 14. The layer 16 is the support for
the patch. Layer 18 provides an adhesive layer for heat sealing the
cover layer 28 around its edges 22. Cover layer 28 is permeable to
gases but not liquids and attached to layer 18 at its edges 22.
This type of label or patch is generally disclosed in U.S. Pat. No.
6,139,935-Cullen where the formation of oxygen absorbing labels is
disclosed. The formation of label or patch of the instant invention
is similar except that the absorbent material is suitable for
absorbing biogenic amines not for absorbing oxygen. The unreactive
or oxidizing absorber for biogenic amines 24 is shown as particles
within a fibrous material 26 such as filter paper. The material may
be either a solid particle such as activated carbon or molecular
sieve for the solid particle or may be an oxidizer such as hydrogen
peroxide absorbed onto a carrier such as filter paper. It is noted
that although the particles are shown as embedded in a fibrous
material the oxidizers such as hydrogen peroxide would be a liquid
that is absorbed onto the fibrous material. Solid particles of
activated carbon could be placed under cover 22 as loose particles.
Generally, it is preferred that solid particles be held in some
sort of material to prevent their dispersal if their container is
ripped.
[0019] In another embodiment, the invention includes a biogenic
releasable absorbing composition including an absorber that will
releasably retain the biogenic amine and an oxidizer that will
react with the biogenic amine to irreversibly retain the biogenic
amine. The oxidizer will react with the biogenic amine to convert
the biogenic amine into another compound that cannot later be
released back into the package. In operation, the releasable
absorber draws the biogenic amine into the composition and the
oxidizer absorber reacts with the biogenic amine to form a new
compound from which the biogenic amine is not released.
[0020] The releasable absorber may be any substance that will
releasably retain the biogenic amine. The releasable absorber
preferably is a porous structure that allows for retention of the
biogenic amine in its pores. Releasable absorbers usable in the
invention include, but are not limited to, activated carbon and
silica gel.
[0021] The releasable absorber may remove the biogenic amine from a
headspace of a container. However, the releasable absorber can lead
to subsequent release of the biogenic amine. Thus, preferred
embodiments of the invention utilize an oxidizer material that
irreversibly reacts with the biogenic amine.
[0022] Illustrated schematically in cross-section FIG. 2 is a
sachet 30 that could be used in a package as a biogenic amines
absorber. The sachet 30 has a cover 32 which is water impermeable
and gas permeable. The sachet is sealed at 34 and 36, and formed
from either a tubular sheet member or flat sheet that has been
folded over and sealed to form a tube. The tube is filled with the
biogenic amine absorber prior to both of the ends being sealed. The
absorber shown as particles 38 which may be activated carbon or
molecular sieve particles. An oxidizer such as hydrogen peroxide
could be absorbed in a fibrous absorbent cellulose member such as
the cellulose member 26 utilized in FIG. 1.
[0023] FIG. 3 is a package 40 for preparing a protein material such
as fish 46 for display or shipping prior to sale. The package
comprises a covering 42 that is the outer covering of the package.
The covering comprises a bag 42 that is sealed shut at 48. The
package 48 has a patch or label 10 fastened to the surface of the
covering bag 42. The fish is carried in tray 44. After the fish 46,
tray 44, and patch 10 have been placed into the covering it is
sealed at 48. While illustrated as having the large space for gas
the bag would likely be subjected to vacuum or a modified
atmosphere in the bag to lower oxygen content to slow decay and
result in closely wrapped fish or other protein material.
Conventional packing cannot eliminate oxygen coming from the
protein and some decay is caused by enzymes. The biogenic amine
unreactive absorber 10 will absorb amines given off by the fish and
lengthen the time when the fish is suitable for consumer use as it
does not have significant odor. Unreactive absorbers will absorb
biogenic amines, but do not react with the biogenic amine. The
unreactive absorbers will largely remove biogenic amines from the
consumer package. By "largely remove" it is meant that the biogenic
amines are not objectionable to the consumer when the package is
opened. The level of biogenic amines not objectionable will vary
depending on the particular protein being stored and what biogenic
amine is being given off.
[0024] FIG. 4 is a schematic cross-section of a package 50 for fish
or other protein with biogenic amines given off from this protein
being absorbed by sachet 30. With the exception of the use of the
sachet instead of the patch or label 10 the FIG. 4 package is
similar to the FIG. 3 package.
[0025] While the permeable container of the invention that holds
the biogenic amines absorber has been illustrated as either a
sachet 30 or a label or patch 10 the invention is not limited to
these particular containers for biogenic amine absorbers. The
container also could be a permeable tube or a container that has
one permeable side. It further could be formed of a polymer strip
that had biogenic amines absorber embedded strip.
[0026] The covering used in the package may be any polymer material
that provides good oxygen barrier properties for the food inside.
Typical of such materials are polycarbonate, and polyvinyl
alcohols, lactic acid polymers, polyesters and polypropylene. A
preferred material is polyethylene, particularly low density
polyethylene because it is low in cost and has good barrier
properties.
[0027] The covering for the package may be wrapped onto the package
and sealed, it may be a bag that is sealed, or may be a tube that
is sealed at both ends. The formation of sealed air tight food
packages is well known.
[0028] The water impermeable air permeable covering for at least a
portion of the sachet, container or label of the invention may be
any material that will pass the amines and inhibits passage of
water or other liquids. Typical of such materials are microporous
spun bonded materials and microporous materials formed by
stretching a voided material. A preferred material is a spun bonded
polyolefin material such as the well-known Tyvek trademark
material.
[0029] Biogenic amines such as trimethylamine are synthesized by
decaying animal, plant and enzymatic metabolisms, and consequently
are found in a wide variety of food products. Biogenic amine
formation is initially the result of protein breakdown. Biogenic
amines are related to food safety and food quality issues, as some
biogenic amines are associated with several acute adverse reactions
in consumers. All protein rich foods subjected to the conditions
that allow bacterial development and activity are expected to
accumulate certain amounts of biogenic amines. Biogenic amines are
in fresh meats, fresh meat products, cooked meat products, cured
meat products and fermented meat products. Biogenic amines are also
found in chesses, tofu, alcoholic beverages, chocolate, sour cream,
yogurt, beans, peas, sauerkraut, some fruits, some nuts, and fish.
Some of the biogenic amines are trimethylamine, tyramine,
tryptamine, phenylamine, histamine, putrescine, phenylethylaminne,
agmatine, spermidine, spermine and cadaverine. Fish has been
rejected by taste panels in the range of 3.0-9.5 mg/100. grams
(3-9.5 ppm) of trimethylamine in fish. Trimethylamine gives fish
the pungent fishy odor. The human odor detection threshold of
trimethylamine is 0.00026-2.1 mg/m3 (0.00026-2.1 ppm). Because the
threshold of detection is so low, this unpleasant odor becomes
apparent long before the wholesomeness of the food is compromised.
It is desirable therefore to reduce the biogenic amine odor so that
the product is not rejected by the consumer prematurely. This is
why common culinary practice is to sprinkle lemon juice on a fish
fillet, for instance, or to serve a wedge of lemon for the diner's
use if they want to reduce the fishy odors.
[0030] The packages of the invention will reduce the biogenic amine
to below the level a human finds unpleasant and off-putting. For a
closely wrapped fish the absorbers of the invention will reduce the
biogenic amines after 7 days of refrigerated storage to a level
that is acceptable to consumers. The level is suitably less than 10
ppb biogenic amine. A preferred level of less than 3 ppm is
obtainable for a closely wrapped piece of fish after 7 days
refrigerated storage. Closely wrapped means not baggy or loose. The
gas space is much less that the protein space in a closely wrapped
package. For biogenic amines given off by foods, other than fish,
amounts somewhat greater than 5 ppb are not objectionable and
greater amounts of these biogenic amines are acceptable to the
consumer.
[0031] The oxidizer may be any material that will oxidize biogenic
amines from the atmosphere. Typical of such oxidizers are hydrogen
peroxide, sodium chlorite, sodium perchlorate, sodium chlorate,
sodium hypochlorite, calcium hypochlorite, sodium chlorate, and
potassium permanganate. The preferred oxidizers are hydrogen
peroxide and sodium chlorite as they rapidly oxidize vaporous
biogenic amines and are safe for use with foods.
[0032] Any unreactive biogenic amine absorber may be utilized that
it is substantially unreactive with biogenic amines. Typical of
such materials are activated carbon, silica gel, molecular sieve
and clay. Suitable materials are molecular sieve and feldspar.
Preferred nonreactive absorbers are activated carbon and silica gel
as they absorb biogenic amines in high amounts and are safe for use
with foods.
[0033] Any amount of unreactive absorbent or oxidizer may be used
that is effective in a particular package. The amount needed varies
with the type of protein packages and the absorber as well as how
much protein is packaged.
[0034] An objective of the invention is to formulate an unreactive
absorber or oxidizer for biogenic amine absorbers that will absorb
and react with the biogenic amines that are formed, eliminating the
off taste and off odor of the food thereby increasing the shelf
life and quality of the food product. The oxidizer could be used
alone or adsorbed onto an adsorbent such as blotting paper. This
would allow the biogenic amine to be irreversibly adsorbed and
neither the food product nor consumer would not be in contact with
the actual reactant. The hydrogen peroxide could be absorbed in an
unreactive absorber particle such as activated carbon or silica
gel.
EXAMPLES
[0035] The following examples are illustrative but not exhaustive
of embodiments of the invention. Parts and percentages are by
weight unless otherwise indicated.
[0036] In Examples 1-13 an 11.times.16 inch foil laminated pouch
was used to test efficacy of the biogenic amine adsorbers. Inside
of the foil pouch was placed a small Tyvek packet with the adsorber
material along with a moisture source which was 0.4 grams of water
on blotter paper. If the adsorber was a liquid oxidizer such as
hydrogen peroxide then the adsorber was put on blotter paper inside
of a packet and placed inside of the foil pouch with the moisture
source. This foil pouch was then vacuumed, heated sealed and filled
with three liters of gas containing 10 ppm of trimethylamine. Blank
foil pouches were also filled with the trimethylamine containing
gas to be used as a standard. The blanks were determined to contain
12,000 and 13,000 ppb trimethylamine for the 7 day test at room
temperature. For the 15 day test the blanks were determined to
contain 4,500 and 5,200 ppb of trimethylamine at room temperature
at the beginning of the test. After 7 days or 15 days an outside
analytical laboratory measured the trimethylamine content of the
foil pouch. The analytical method used was microextraction gas
chromatography mass spectroscopy. 5 ppb is the detection limit of
the analytical method for trimethylamine.
[0037] The following are test results:
Example 1
[0038] 2.0 grams of dry activated carbon with a moisture source
reduced the trimethylamine content to 870 ppb in 7 days at room
temperature.
Example 2
[0039] 2.0 grams of dry activated carbon without a moisture source
reduced the trimethylamine content to less than 5 ppb in 7 days at
room temperature.
Example 3
[0040] 2.0 grams of 13.times. molecular sieve reduced the
trimethylamine content to less 1,400 ppb in 7 days at room
temperature.
Example 4
[0041] 2.0 grams of 300 angstrom silica gel impregnated with 0.5
grams of moisture reduced the trimethylamine content to less than 5
ppb after 7 days at room temperature.
Example 5
[0042] 2.0 grams of 13.times. molecular sieve reduced the
trimethylamine content to 8 ppb in 15 days at room temperature.
Example 6
[0043] 2.0 grams of 300 angstrom silica gel impregnated with 0.5
grams of water reduced the trimethylamine content to less than 5
ppb in 15 days at room temperature.
Example 7
[0044] 6.6 grams of 3% hydrogen peroxide (0.0058 moles) on blotter
paper reduced the trimethylamine content to 16 ppb in 15 days at
room temperature.
Example 8
[0045] 0.7 grams of 35% hydrogen peroxide (0.0072 moles) on blotter
paper reduced the trimethylamine content to 100 ppb in 15 days at
room temperature.
Example 9
[0046] 0.5 grams of sodium chlorite reduced the trimethylamine
content to less than 5 ppb in 7 days at room temperature.
[0047] The above Examples show the effectiveness of a variety of
unreactive absorbers and oxidizers.
[0048] The invention has been described in detail with particular
reference to a presently preferred embodiment, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention. The presently disclosed
embodiments are therefore considered in all respects to be
illustrative and not restrictive. The scope of the invention is
indicated by the appended claims, and all changes that come within
the meaning and range of equivalents thereof are intended to be
embraced therein.
* * * * *