CA2230504C - Low-nitrite composition for curing meat and process for preparing low-nitrite cured meat products - Google Patents
Low-nitrite composition for curing meat and process for preparing low-nitrite cured meat products Download PDFInfo
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- CA2230504C CA2230504C CA002230504A CA2230504A CA2230504C CA 2230504 C CA2230504 C CA 2230504C CA 002230504 A CA002230504 A CA 002230504A CA 2230504 A CA2230504 A CA 2230504A CA 2230504 C CA2230504 C CA 2230504C
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/02—Preserving by means of inorganic salts
- A23B4/027—Preserving by means of inorganic salts by inorganic salts other than kitchen salt, or mixtures thereof with organic compounds, e.g. biochemical compounds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/02—Preserving by means of inorganic salts
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Abstract
A low-nitrite composition for curing meat comprising: (i) a nitrite, (ii) a pigment and (iii) an antioxidant. The composition confers to cured meat colour characteristics which compare favourably to full-nitrite cured meat obviating the disadvantages of full-nitrite cured meat. Further disclosed is a process for preparing a low-nitrite cured meat product comprising the steps of: (i) adding to a meat product an effective amount of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant; (ii) distributing the meat curing composition substantially evenly throughout the meat product; and (iii) processing the meat product having the meat curing composition distributed therein. Still further disclosed is a process for preparing low-nitrite cured solid meat product comprising the steps of: (i) preparing a dispersion of a low-nitrite meat curing composition comprising an effective amount of sodium nitrite, a pigment and an antioxidant; (ii) injecting the dispersion into a solid meat product;
and (iii) physically treating the solid meat product; and (iv) processing the solid meat product having the meat curing composition distributed therein.
and (iii) physically treating the solid meat product; and (iv) processing the solid meat product having the meat curing composition distributed therein.
Description
WO 97/07683 ' 1PCT/CA96/00573 , 5 TI;CIiNIC L FIBLD
The present invention relates generally to meat-curing compositions.
More particularly, the present invention relates to a low-nitrite composition for curing meat and to a process for preparing low-nitrite cured meat products.
BACI~GROLTND A_R_T
Historically, meat curing practice, being founded upon the ancient art of preserving meat with salt, employed the use of sodium nitrite along with sugar, salt, various reducing agents and phosphates to cure meat.
The role of nitrite in meat curing was believed to be at least three-fold:
(i) it produces the characteristic pink-red cured-meat pigment, dinitrosyl ferrohemochrome; (ii) it gives oxidative stability to the meat to prevent lipid oxidation thereby enhancing the cured-meat flavour; and (iii) it inhibits the outgrowth of a number of food-poisoning and spoilage bacteria, for example Clostridium botulinum. It was also known that nitrite is not unique in imparting oxidative stability or in its antimicrobial effect.
While performing all the above-stated functions well, it was established that nitrite also has some serious drawbacks. I~or example, it forms carcinogenic nitrosamines in meat, especially nitrosopyrrolidine and dimethylnitrosamine, in the parts per billion range. Ol~a ingestion, nitrites may cause the formation of nitrosamines in the stomach. Further, nitrites may enhance the carcinogenic action of N-nitroso-N-methylbenzylamine in the formation of esophageal tumours. Accordingly, it was the stated policy of the Canadian and United States governments to support the search for a substitute.
The likelihood of fording a molecule which duplicates all the functions of nitrite is small, therefore, research at the University of Toronto has focused on devising a mufti-component system for curing meats which, as a whole, would duplicate all the functions of nitrite. To that end various compounds were discovered which would reproduce the antioxidant and antimicrobial functions of nitrite. However, by far the largest difficulty of nitrite-free meat curing is the reproduction of the characteristic cured meat colour usually conferred by nitrite. Thus, much of the prior art has been directed to identifying compounds which would confer to cured meat, the meat colour characteristic of nitrite.
United States patent number 4,559,234 to Rubin et al. (Rubin), describes a nitrite-free composition for curing meats, which comprises dinitrosyl ferrohemochrome (DNFH), an antioxidant, a sequestering agent and an antimicrobial agent. Curing of meats with the preferred embodiments of the composition described in Rubin produces an essentially nitrite-free meat product, substantially indistinguishable in colour and flavour from nitrite cured meat.
DNFH may be obtained synthetically from hemin prepared from the haemoglobin in blood, by reaction with nitric oxide in the presence of a reducing agent. See, for example, Shahidi et al., J. Food Sc., 50: 272 (1985).
However, DNFH is very susceptible to light-induced oxidation and subsequent fading. Even when stored in the dark in oxygen-free conditions, its shelf life is not greater than about four to five weeks. Moreover, DNFH is a fine crystalline solid which is only sparingly soluble in either water or curing brine.
Consequently, it is a difficult material to handle. Further, it is difficult to achieve a uniform distribution of DNFH within an intact cut of meat, because it is so slightly soluble in injectable aqueous solutions. These factors constitute technical drawbacks to the system and processes described in Rubin.
Recent attempts have been made to overcome some of these difficulties by encapsulating DNFH in a polysaccharide or the like. See, for example, O'Boyle et al., J. Food Sc., 57(4), 807 (1992) and published Canadian patent application number 2,023,966. Encapsulated DNFH has proven to have an extended shelf like, and its increased dispersability in pickle solution allows for a more even dispersion of colour when injected into intact cut meat.
The present invention relates generally to meat-curing compositions.
More particularly, the present invention relates to a low-nitrite composition for curing meat and to a process for preparing low-nitrite cured meat products.
BACI~GROLTND A_R_T
Historically, meat curing practice, being founded upon the ancient art of preserving meat with salt, employed the use of sodium nitrite along with sugar, salt, various reducing agents and phosphates to cure meat.
The role of nitrite in meat curing was believed to be at least three-fold:
(i) it produces the characteristic pink-red cured-meat pigment, dinitrosyl ferrohemochrome; (ii) it gives oxidative stability to the meat to prevent lipid oxidation thereby enhancing the cured-meat flavour; and (iii) it inhibits the outgrowth of a number of food-poisoning and spoilage bacteria, for example Clostridium botulinum. It was also known that nitrite is not unique in imparting oxidative stability or in its antimicrobial effect.
While performing all the above-stated functions well, it was established that nitrite also has some serious drawbacks. I~or example, it forms carcinogenic nitrosamines in meat, especially nitrosopyrrolidine and dimethylnitrosamine, in the parts per billion range. Ol~a ingestion, nitrites may cause the formation of nitrosamines in the stomach. Further, nitrites may enhance the carcinogenic action of N-nitroso-N-methylbenzylamine in the formation of esophageal tumours. Accordingly, it was the stated policy of the Canadian and United States governments to support the search for a substitute.
The likelihood of fording a molecule which duplicates all the functions of nitrite is small, therefore, research at the University of Toronto has focused on devising a mufti-component system for curing meats which, as a whole, would duplicate all the functions of nitrite. To that end various compounds were discovered which would reproduce the antioxidant and antimicrobial functions of nitrite. However, by far the largest difficulty of nitrite-free meat curing is the reproduction of the characteristic cured meat colour usually conferred by nitrite. Thus, much of the prior art has been directed to identifying compounds which would confer to cured meat, the meat colour characteristic of nitrite.
United States patent number 4,559,234 to Rubin et al. (Rubin), describes a nitrite-free composition for curing meats, which comprises dinitrosyl ferrohemochrome (DNFH), an antioxidant, a sequestering agent and an antimicrobial agent. Curing of meats with the preferred embodiments of the composition described in Rubin produces an essentially nitrite-free meat product, substantially indistinguishable in colour and flavour from nitrite cured meat.
DNFH may be obtained synthetically from hemin prepared from the haemoglobin in blood, by reaction with nitric oxide in the presence of a reducing agent. See, for example, Shahidi et al., J. Food Sc., 50: 272 (1985).
However, DNFH is very susceptible to light-induced oxidation and subsequent fading. Even when stored in the dark in oxygen-free conditions, its shelf life is not greater than about four to five weeks. Moreover, DNFH is a fine crystalline solid which is only sparingly soluble in either water or curing brine.
Consequently, it is a difficult material to handle. Further, it is difficult to achieve a uniform distribution of DNFH within an intact cut of meat, because it is so slightly soluble in injectable aqueous solutions. These factors constitute technical drawbacks to the system and processes described in Rubin.
Recent attempts have been made to overcome some of these difficulties by encapsulating DNFH in a polysaccharide or the like. See, for example, O'Boyle et al., J. Food Sc., 57(4), 807 (1992) and published Canadian patent application number 2,023,966. Encapsulated DNFH has proven to have an extended shelf like, and its increased dispersability in pickle solution allows for a more even dispersion of colour when injected into intact cut meat.
3 ~ PCT/Ct~96/00573 Although the use of encapsulated DNFH in a nitrite-free, curing composition produces a cured meat product that has acceptable colour, the ' nitrite-free meat product is usually darker in colour (i.e. characterized by lower L values) when compared to a full-nitrite cured meat product. The relatively low L values of the nitrite-free meat product are believed to be due to the different modes of action between full-nitrite and nitrite-free curing systems.
Nitrite converts the native muscle pigment, myoglobin, into the nitroso-derivative which acts as a pink pigment. In contrast, the added DNFH pigment provides the characteristic cured-meat colour and at the same time has tv mask the non-nitrosated pigments originally present in the meat. This is a fundamental problem with a nitrite-free meat curing system. In a nitrite-free cured meat product, there is no compound which will nitrosate the indigenous myoglobin in the meat. Thus, as the meat is cooked and/or subject to a smoking process, myoglobin is denatured to produce a derivative:
metmyochromogen. Metmyochromogen is the source of the brownish, dark background which is only partially masked by the DNFH.
Thus, in summary, while the prior art has provided a number of DNFH-based systems as substitutes for nitrite-based meat curing systems, in practice none of the DNFH-based systems are able to convey meat colour characteristics which are the same as or improved over those conveyed by nitrite-based meat curing systems. Further, some of the prior art curing systems have utility which is restricted to situations where there exists a limited amount of pigmentation (i.e. myoglobin).
It would be desirable to have a meat curing composition which is both (i) free of the deleterious effects of nitrites and (ii) capable of producing a bright cured meat colour in virtually all meat regardless of the levels of myoglobin present in the meat, thereby constituting an improvement over currently available DNFH-based curing systems.
._ I?ISCT_.O~LTRF OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one a of the disadvantages of the prior art.
Accordingly, in one of its aspects, the present invention provides a low-s nitrite composition for curing meat comprising: (i) a nitrite, (ii) a pigment, and (iii) an antioxidant.
In another of its aspects, the present invention provides a process for preparing a low-nitrite cured meat product comprising the steps of:
(i) adding to a meat product an effective amount of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant;
(ii) distributing the meat curing composition substantially evenly throughout the meat product; and (iii) processing the meat product having the meat curing composition distributed therein.
In yet another of its aspects, the present invention provides a process for preparing low-nitrite cured solid meat product comprising the steps of:
(i) preparing a dispersion of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant;
(ii) injecting the dispersion into a solid meat product; and (iii) physically treating the solid meat product; and (iv) processing the solid meat product having the meat curing composition distributed therein.
Applicant has surprisingly and unexpectedly discovered that an improved meat curing composition can be made using low levels of nitrite.
More specifically, it has been discovered that the cured meat colour characteristics of nitrite can be conveyed using nitrite at low levels which do ' not result in the deleterious effects of conventional high levels of nitrite discussed above. The antimicrobial and antioxidant characteristics of nitrite are prevalent only at conventionally high levels of nitrite. Thus, by maintaining a low level of nitrite and supplementing this with an antioxidant agent and, optionally, an antimicrobial agent, an improved meat curing composition is obtained which is substantially free of the deleterious effects of conventional f levels of nitrite yet is able to convey the cured meat colour characteristics of nitrite. Further, a meat product cured with the present low-nitrite composition is characterized by being substantially free of residual nitrite. Practically, this translates into less than 1 ppm residual nitrite deternuned by AOAC Official Method 24.044.
Accordingly, the present invention relates to a low-nitrite meat curing composition which can be used to produce a meat product which has a substantially identical appearance to full-nitrite cured meat product. The improved appearance of the meat product derived from the present low-nitrite meat curing composition is believed to be due to the combined action of the small amount of the nitrite and the pigment, particularly the pigment dinitrosyl ferrohemochrome. The meat product produced utilizing the present low-nitrite curing composition is characterized by being substantially free of residual nitrite. The low-nitrite meat composition can be also used to induce a typical cured meat colour in meat products based on meat, poultry, or fish that is low in myoglobin and is therefore light in colour.
BEST MODE FOR. CARRYING OUT THE INVEN ION
As used throughout this specification, the term "low-nitrite" is intended to mean an amount of nitrite to be utilized in a meat-curing process which is less than the amount of nitrite conventionally added to the meat to be cured -practically, this generally encompasses the use of less than about 80, preferably less than about 25, more preferably from about 1 to about 25, most preferably from about 2 to about 10, milligrams per kilogram of meat to be cured. The " term "full-nitrite" is intended to mean an amount of nitrite which is necessary to convey to meat: (i) the characteristic pink-red colour, (ii) oxidative stability, and (iii) the antimicrobial effect discussed above - practically, this generally encompasses the use of from about 80 to about 200 milligrams per kilogram of meat to be cured. In many jurisdictions, 80 to 120 ppm is the minimum level prescribed by law. The term "nitrite-free" is meant to encompass a product in which no nitrite has been added during the curing process.
The low-nitrite composition of the present invention comprises: (i) nitrite, (ii) a pigment and (iii) an antioxidant. The nitrite is present in an amount which is sufficient to react with the myoglobin in the meat thereby leaving substantially no residual nitrite after processing is complete. The choice of nitrite is not particularly restricted provided, of course, that it is non-toxic to the consumer of the meat product. Non-limiting examples of suitable nitrites include sodium nitrite, potassium nitrite and mixtures thereof. The most preferred nitrite for using in the present invention is sodium nitrite. It is believed that the low level of nitrite which is added reduces the concentration of metmyochromogen (the brown coloured oxidation product of myoglobin), and thus, the intensity of the brownish background which the pigment must conceal to provide the desired colour.
The other component of the present low-nitrite composition is a pigment. The pigment is selected on the basis that it useful as a non-toxic food additive and can conceal the characteristic brown colour of metmyochromogen.
Non-limiting examples of suitable pigments may be selected from the group comprising dinitrosyl ferrohemochrome (hereinafter also referred to as "DNFH"), natural and synthetic pigments derived from vegetable and fungal sources (e.g. beets) and mixtures thereof. The most preferred pigment for use in the present low-nitrite composition is DNFH.
As discussed above, it is known that DNFH is susceptible to light induced oxidation and subsequent fading with the result that its utility as a pigment is reduced significantly. Accordingly, it is preferred that the DNFH
used in the low-nitrite composition is encapsulated. The encapsulation process for preparing the microcapsules of DNFH may be conducted by many of the encapsulation processed known in the art, but the preferred method is a spray-drying process to produce microcapsules as described in O'Boyle et al., J.
Food Sc., 57(4), 807, 1992 and Canadian patent application number 2,023,966. The -7_ encapsulating material is preferably a natural film-forming polymer, more f preferably a polysaccharide or carbohydrate. Specific non-limiting examples of preferred materials include beta-cyclodextrin, starch, modified starch, dextrin, maltodextrin (e.g. N-LokTM (National Starch and Chemical Corp., Bridgewater, N.J.)) and proteins such as gelatin, gum arabic, carboxymethyl cellulose and the like. The DNFH generally constitutes from 0.5-S % by weight, preferably from about 1-3 % by weight, of the microcapsules.
Of course, those of skill in the art will recognize that it is not critical that the preferred pigment, DNFH, be encapsulated prior to use. For example, it is possible, although less preferred, to use freshly produced DNFH or DNFH
which has been protected by another technique such as freezing, cryogenic cooling and the like.
As discussed above, present low-nitrite composition comprises low levels of nitrite. Practically, the nitrite is used in an amount of less than about 80, preferably less than about 25, more preferably from about 1 to about 25, most preferably from about 2 to about 10, milligrams per kilogram of meat to be cured. Preferably, the amount of pigment used iii the present low-nitrite composition is less than 100, more preferably in the range of from about 10 to about 60, most preferably in the range of from about 20 to about 35, milligrams per kilogram of meat to be cured.
The present low-nitrite composition further comprises at least one antioxidant. Suitable antioxidants are those commonly used in food systems.
A non-limiting example of a suitable antioxidant may be selected from the group comprising ascorbic acid, physiologically acceptable salts of ascorbic acid such as sodium ascorbate, ascorbyl palinitate, erythorbic acid, ascorbyl acetal; phenolic antioxidants such as butylated hydroxy anisole (BHA), ' butylated hydroxytoluene (BHT), t-butylhydroquinone (TBHQ), propyl gallate, s nordihydroguaiaretic acid; and d,l-alpha-tocopherol, lecithin, dilauryl thiodiproprionate, natural antioxidants such as deflavourized rosemary spice extract and mixtures thereof. Selection of a suitable antioxidant is considered to be within the purview of a person skilled in the art. The amount of _$_ antioxidant used is in accordance with good manufacturing practice when the antioxidant is ascorbic acid or a derivative thereof, the amount of antioxidant used is preferably in the range of from about 100 to about 1000, more preferably from about 500 to about 600, milligrams per kilogram of meat to be , cured. When the antioxidant is phenolic, the amount of antioxidant used is preferably in the range of from about 10 to about 200, more preferably from about 30 to about 150. When the antioxidant is d,l-alpha-tocopherol, the amount of antioxidant used is preferably up to about 1500. When the antioxidant is rosemary spice extract, the amount of antioxidant used is preferably in the range of from about 500 to about 30,000.
Optionally, and preferably, the present low-nitrite composition further comprises at least one sequestering agent. As is known in the art, a sequestering agent is used for the purpose of enhancing lipid stability. A non-limiting example of a suitable sequestering agent may be selected from the group comprising monosodium phosphate, disodium phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium citrate, citric acid, monoglyceride citrate, 8-hydroxyquinoline, sodium gluconate, catechol, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, diethylenetriamine pentaacetic acid, salicylic acid and mixtures thereof. Certain of these sequestering agents, for example disodium ethylenediamine tetracetate, can contribute to the oxidative stability of the present low-nitrite composition. Preferably, when used in the present low-nitrite composition, the sequestering agent is utilized as a separate ingredient.
If the sequestering agent is free of phosphate, it is preferably used in an amount in the range of from about 10 to about 1000 milligrams per kilogram of meat to be cured (i.e. ppm). If the sequestering agent contains phosphate, it is preferably used in an amount in the range of from about 1000 to about 6000 ' milligrams per kilogram of meat to be cured. Selection of a suitable sequestering agent is considered to be within the purview of a person skilled in the art.
WO 97/07683 ~ ~ PCT/CA96/00573 Optionally, the present low-nitrite composition further comprises at least one antimicrobial agent. A non-limiting example of a suitable antimicrobial agent may be selected from the group comprising sodium hypophosphite, potassium sorbate, lactic acid-producing bacteria, sodium lactate, 3-(4-tolyl S sulfonyl)acrylonitrile, raisin, propylparahydroxybenzoate, methyl fumarate, dimethyl fumarate, ethyl fumarate, diethylfumarate and mixtures thereof.
Generally, the antimicrobial agent may be used in an amount in the range of from about SO to about 5000 milligrams per kilogram meat to be cured.
Optimum amounts are dependent on the choice of antimicrobial agent, and selection is considered to be within the purview of a person skilled in the art.
The present low-nitrite composition can be incorporated readily into a process for the production of cured meat. For example, in the production of comminuted meat products such as wieners, the present low-nitrite composition comprising sodium nitrite (preferred nitrite), encapsulated DNFH (preferred pigment) and an antioxidant may be added at virtually any point in the production process. When the present low-nitrite composition comprises sodium nitrite, encapsulated DNFH, an antioxidant, a sequestering agent and an antimicrobial agent, the composition may be supplied as a preformed mixture or kit in appropriate size and proportions, which then needs only to be thoroughly mixed into the meat emulsion with oxygen exclusion. The resultant meat product, after processing (i.e. cooking and packaging), is substantially identical in taste and colour to a similarly prepared full-nitrite cured product.
In an alternative embodiment, the present low-nitrite composition may be applied to solid cuts of meat so as to prepare, for example, low-nitrite hams, bacon and cured poultry products of a similar nature. In this embodiment, the present low-nitrite composition is initially dispersed in a pickle solution.
The nature of the pickle solution is not particularly restricted and within the purview of a person skill in the art. For example, and by way of illustration only, a suitable pickle solution may comprise appropriate levels of the following ingredients such that the concentration of each ingredient based on the weight total weight of the meat product (i.e. meat and additives) is as indicated:
about WO 97/07683 ' PCT/CA96/00573 2 % salt; about 1 % sugar; about 0.3 % phosphate sequestering agent; about 0.06 % sodium ascorbate and/or appropriate antioxidant; and an appropriate amount of antimicrobial agent. The nitrite/DNFHlantioxidant/pickle dispersion is then preferably treated with a means to reduce the particle size of the DNFH
which tends to agglomerize in the pickle solution. Practically, this can be achieved by mixing or by use of a homogenizer such as a polytron homogenizer. Care should be exercised to substantially prevent contact of the dispersion with oxygen during particle size reduction. Practically, this is achieved by conducting particle size reduction of the dispersion in an inert atmosphere such as nitrogen. After particle size reduction of the DNFH, the dispersion is injected into the meat by conventional means. For example, it is possible to use an injection needle having a plurality of outlet ports provided in the needle stem side wall and directed radially away from the needle stem.
Such an injection needle can be used in conjunction with suitable a pump. By such a technique, which is conventional in the art, one can obtain total perfusion of the meat product, with substantially even distribution of the present low-nitrite composition throughout the solid meat, to give a substantially uniform colour throughout the cross-section of the meat product.
It is preferred to subject the meat to a treatment step which includes tumbling or massaging. Generally, the treatment is conducted of a period of from about 2 to about 4 hours in a vacuum or an atmospheric tumbler. Such tumblers are conventional in the art. Treatment of the meat in this manner has the effect of rendering the muscle sheathes therein less resistant to penetration by the nitrite and DNFH, thereby enhancing dispersion of the latter.
After injection of low-nitrite composition, the meat is subjected to a step of physical treatment such as kneading, tumbling or massaging to facilitate dispersion of the pigment evenly throughout the meat. The step of physical treatment may, for example, utilize a vacuum or atmospheric rotary tumbler for a period of from about 9 to about 18 hours at a rotational speed of from about 10 to about 15 rpm. Those of skill in the art will recognize that types of physical treatment may be used to achieve substantially the same effect.
In this manner, a low-nitrite product, with a uniform colour which is virtually indistinguishable from that of a full-nitrite cured product, is obtained.
The invention will be further described with reference to the following Examples, which are provided for illustrative purposes only and should not be used to limit the scope of the invention.
In the Examples, all chemicals used for analytical work were reagent grade and were obtained from major chemical suppliers. Unless otherwise indicated, all parts are parts by weight.
Example 1 - Synthesis and Microencapsulation of DNFH
Nitrite converts the native muscle pigment, myoglobin, into the nitroso-derivative which acts as a pink pigment. In contrast, the added DNFH pigment provides the characteristic cured-meat colour and at the same time has tv mask the non-nitrosated pigments originally present in the meat. This is a fundamental problem with a nitrite-free meat curing system. In a nitrite-free cured meat product, there is no compound which will nitrosate the indigenous myoglobin in the meat. Thus, as the meat is cooked and/or subject to a smoking process, myoglobin is denatured to produce a derivative:
metmyochromogen. Metmyochromogen is the source of the brownish, dark background which is only partially masked by the DNFH.
Thus, in summary, while the prior art has provided a number of DNFH-based systems as substitutes for nitrite-based meat curing systems, in practice none of the DNFH-based systems are able to convey meat colour characteristics which are the same as or improved over those conveyed by nitrite-based meat curing systems. Further, some of the prior art curing systems have utility which is restricted to situations where there exists a limited amount of pigmentation (i.e. myoglobin).
It would be desirable to have a meat curing composition which is both (i) free of the deleterious effects of nitrites and (ii) capable of producing a bright cured meat colour in virtually all meat regardless of the levels of myoglobin present in the meat, thereby constituting an improvement over currently available DNFH-based curing systems.
._ I?ISCT_.O~LTRF OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one a of the disadvantages of the prior art.
Accordingly, in one of its aspects, the present invention provides a low-s nitrite composition for curing meat comprising: (i) a nitrite, (ii) a pigment, and (iii) an antioxidant.
In another of its aspects, the present invention provides a process for preparing a low-nitrite cured meat product comprising the steps of:
(i) adding to a meat product an effective amount of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant;
(ii) distributing the meat curing composition substantially evenly throughout the meat product; and (iii) processing the meat product having the meat curing composition distributed therein.
In yet another of its aspects, the present invention provides a process for preparing low-nitrite cured solid meat product comprising the steps of:
(i) preparing a dispersion of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant;
(ii) injecting the dispersion into a solid meat product; and (iii) physically treating the solid meat product; and (iv) processing the solid meat product having the meat curing composition distributed therein.
Applicant has surprisingly and unexpectedly discovered that an improved meat curing composition can be made using low levels of nitrite.
More specifically, it has been discovered that the cured meat colour characteristics of nitrite can be conveyed using nitrite at low levels which do ' not result in the deleterious effects of conventional high levels of nitrite discussed above. The antimicrobial and antioxidant characteristics of nitrite are prevalent only at conventionally high levels of nitrite. Thus, by maintaining a low level of nitrite and supplementing this with an antioxidant agent and, optionally, an antimicrobial agent, an improved meat curing composition is obtained which is substantially free of the deleterious effects of conventional f levels of nitrite yet is able to convey the cured meat colour characteristics of nitrite. Further, a meat product cured with the present low-nitrite composition is characterized by being substantially free of residual nitrite. Practically, this translates into less than 1 ppm residual nitrite deternuned by AOAC Official Method 24.044.
Accordingly, the present invention relates to a low-nitrite meat curing composition which can be used to produce a meat product which has a substantially identical appearance to full-nitrite cured meat product. The improved appearance of the meat product derived from the present low-nitrite meat curing composition is believed to be due to the combined action of the small amount of the nitrite and the pigment, particularly the pigment dinitrosyl ferrohemochrome. The meat product produced utilizing the present low-nitrite curing composition is characterized by being substantially free of residual nitrite. The low-nitrite meat composition can be also used to induce a typical cured meat colour in meat products based on meat, poultry, or fish that is low in myoglobin and is therefore light in colour.
BEST MODE FOR. CARRYING OUT THE INVEN ION
As used throughout this specification, the term "low-nitrite" is intended to mean an amount of nitrite to be utilized in a meat-curing process which is less than the amount of nitrite conventionally added to the meat to be cured -practically, this generally encompasses the use of less than about 80, preferably less than about 25, more preferably from about 1 to about 25, most preferably from about 2 to about 10, milligrams per kilogram of meat to be cured. The " term "full-nitrite" is intended to mean an amount of nitrite which is necessary to convey to meat: (i) the characteristic pink-red colour, (ii) oxidative stability, and (iii) the antimicrobial effect discussed above - practically, this generally encompasses the use of from about 80 to about 200 milligrams per kilogram of meat to be cured. In many jurisdictions, 80 to 120 ppm is the minimum level prescribed by law. The term "nitrite-free" is meant to encompass a product in which no nitrite has been added during the curing process.
The low-nitrite composition of the present invention comprises: (i) nitrite, (ii) a pigment and (iii) an antioxidant. The nitrite is present in an amount which is sufficient to react with the myoglobin in the meat thereby leaving substantially no residual nitrite after processing is complete. The choice of nitrite is not particularly restricted provided, of course, that it is non-toxic to the consumer of the meat product. Non-limiting examples of suitable nitrites include sodium nitrite, potassium nitrite and mixtures thereof. The most preferred nitrite for using in the present invention is sodium nitrite. It is believed that the low level of nitrite which is added reduces the concentration of metmyochromogen (the brown coloured oxidation product of myoglobin), and thus, the intensity of the brownish background which the pigment must conceal to provide the desired colour.
The other component of the present low-nitrite composition is a pigment. The pigment is selected on the basis that it useful as a non-toxic food additive and can conceal the characteristic brown colour of metmyochromogen.
Non-limiting examples of suitable pigments may be selected from the group comprising dinitrosyl ferrohemochrome (hereinafter also referred to as "DNFH"), natural and synthetic pigments derived from vegetable and fungal sources (e.g. beets) and mixtures thereof. The most preferred pigment for use in the present low-nitrite composition is DNFH.
As discussed above, it is known that DNFH is susceptible to light induced oxidation and subsequent fading with the result that its utility as a pigment is reduced significantly. Accordingly, it is preferred that the DNFH
used in the low-nitrite composition is encapsulated. The encapsulation process for preparing the microcapsules of DNFH may be conducted by many of the encapsulation processed known in the art, but the preferred method is a spray-drying process to produce microcapsules as described in O'Boyle et al., J.
Food Sc., 57(4), 807, 1992 and Canadian patent application number 2,023,966. The -7_ encapsulating material is preferably a natural film-forming polymer, more f preferably a polysaccharide or carbohydrate. Specific non-limiting examples of preferred materials include beta-cyclodextrin, starch, modified starch, dextrin, maltodextrin (e.g. N-LokTM (National Starch and Chemical Corp., Bridgewater, N.J.)) and proteins such as gelatin, gum arabic, carboxymethyl cellulose and the like. The DNFH generally constitutes from 0.5-S % by weight, preferably from about 1-3 % by weight, of the microcapsules.
Of course, those of skill in the art will recognize that it is not critical that the preferred pigment, DNFH, be encapsulated prior to use. For example, it is possible, although less preferred, to use freshly produced DNFH or DNFH
which has been protected by another technique such as freezing, cryogenic cooling and the like.
As discussed above, present low-nitrite composition comprises low levels of nitrite. Practically, the nitrite is used in an amount of less than about 80, preferably less than about 25, more preferably from about 1 to about 25, most preferably from about 2 to about 10, milligrams per kilogram of meat to be cured. Preferably, the amount of pigment used iii the present low-nitrite composition is less than 100, more preferably in the range of from about 10 to about 60, most preferably in the range of from about 20 to about 35, milligrams per kilogram of meat to be cured.
The present low-nitrite composition further comprises at least one antioxidant. Suitable antioxidants are those commonly used in food systems.
A non-limiting example of a suitable antioxidant may be selected from the group comprising ascorbic acid, physiologically acceptable salts of ascorbic acid such as sodium ascorbate, ascorbyl palinitate, erythorbic acid, ascorbyl acetal; phenolic antioxidants such as butylated hydroxy anisole (BHA), ' butylated hydroxytoluene (BHT), t-butylhydroquinone (TBHQ), propyl gallate, s nordihydroguaiaretic acid; and d,l-alpha-tocopherol, lecithin, dilauryl thiodiproprionate, natural antioxidants such as deflavourized rosemary spice extract and mixtures thereof. Selection of a suitable antioxidant is considered to be within the purview of a person skilled in the art. The amount of _$_ antioxidant used is in accordance with good manufacturing practice when the antioxidant is ascorbic acid or a derivative thereof, the amount of antioxidant used is preferably in the range of from about 100 to about 1000, more preferably from about 500 to about 600, milligrams per kilogram of meat to be , cured. When the antioxidant is phenolic, the amount of antioxidant used is preferably in the range of from about 10 to about 200, more preferably from about 30 to about 150. When the antioxidant is d,l-alpha-tocopherol, the amount of antioxidant used is preferably up to about 1500. When the antioxidant is rosemary spice extract, the amount of antioxidant used is preferably in the range of from about 500 to about 30,000.
Optionally, and preferably, the present low-nitrite composition further comprises at least one sequestering agent. As is known in the art, a sequestering agent is used for the purpose of enhancing lipid stability. A non-limiting example of a suitable sequestering agent may be selected from the group comprising monosodium phosphate, disodium phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium citrate, citric acid, monoglyceride citrate, 8-hydroxyquinoline, sodium gluconate, catechol, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, diethylenetriamine pentaacetic acid, salicylic acid and mixtures thereof. Certain of these sequestering agents, for example disodium ethylenediamine tetracetate, can contribute to the oxidative stability of the present low-nitrite composition. Preferably, when used in the present low-nitrite composition, the sequestering agent is utilized as a separate ingredient.
If the sequestering agent is free of phosphate, it is preferably used in an amount in the range of from about 10 to about 1000 milligrams per kilogram of meat to be cured (i.e. ppm). If the sequestering agent contains phosphate, it is preferably used in an amount in the range of from about 1000 to about 6000 ' milligrams per kilogram of meat to be cured. Selection of a suitable sequestering agent is considered to be within the purview of a person skilled in the art.
WO 97/07683 ~ ~ PCT/CA96/00573 Optionally, the present low-nitrite composition further comprises at least one antimicrobial agent. A non-limiting example of a suitable antimicrobial agent may be selected from the group comprising sodium hypophosphite, potassium sorbate, lactic acid-producing bacteria, sodium lactate, 3-(4-tolyl S sulfonyl)acrylonitrile, raisin, propylparahydroxybenzoate, methyl fumarate, dimethyl fumarate, ethyl fumarate, diethylfumarate and mixtures thereof.
Generally, the antimicrobial agent may be used in an amount in the range of from about SO to about 5000 milligrams per kilogram meat to be cured.
Optimum amounts are dependent on the choice of antimicrobial agent, and selection is considered to be within the purview of a person skilled in the art.
The present low-nitrite composition can be incorporated readily into a process for the production of cured meat. For example, in the production of comminuted meat products such as wieners, the present low-nitrite composition comprising sodium nitrite (preferred nitrite), encapsulated DNFH (preferred pigment) and an antioxidant may be added at virtually any point in the production process. When the present low-nitrite composition comprises sodium nitrite, encapsulated DNFH, an antioxidant, a sequestering agent and an antimicrobial agent, the composition may be supplied as a preformed mixture or kit in appropriate size and proportions, which then needs only to be thoroughly mixed into the meat emulsion with oxygen exclusion. The resultant meat product, after processing (i.e. cooking and packaging), is substantially identical in taste and colour to a similarly prepared full-nitrite cured product.
In an alternative embodiment, the present low-nitrite composition may be applied to solid cuts of meat so as to prepare, for example, low-nitrite hams, bacon and cured poultry products of a similar nature. In this embodiment, the present low-nitrite composition is initially dispersed in a pickle solution.
The nature of the pickle solution is not particularly restricted and within the purview of a person skill in the art. For example, and by way of illustration only, a suitable pickle solution may comprise appropriate levels of the following ingredients such that the concentration of each ingredient based on the weight total weight of the meat product (i.e. meat and additives) is as indicated:
about WO 97/07683 ' PCT/CA96/00573 2 % salt; about 1 % sugar; about 0.3 % phosphate sequestering agent; about 0.06 % sodium ascorbate and/or appropriate antioxidant; and an appropriate amount of antimicrobial agent. The nitrite/DNFHlantioxidant/pickle dispersion is then preferably treated with a means to reduce the particle size of the DNFH
which tends to agglomerize in the pickle solution. Practically, this can be achieved by mixing or by use of a homogenizer such as a polytron homogenizer. Care should be exercised to substantially prevent contact of the dispersion with oxygen during particle size reduction. Practically, this is achieved by conducting particle size reduction of the dispersion in an inert atmosphere such as nitrogen. After particle size reduction of the DNFH, the dispersion is injected into the meat by conventional means. For example, it is possible to use an injection needle having a plurality of outlet ports provided in the needle stem side wall and directed radially away from the needle stem.
Such an injection needle can be used in conjunction with suitable a pump. By such a technique, which is conventional in the art, one can obtain total perfusion of the meat product, with substantially even distribution of the present low-nitrite composition throughout the solid meat, to give a substantially uniform colour throughout the cross-section of the meat product.
It is preferred to subject the meat to a treatment step which includes tumbling or massaging. Generally, the treatment is conducted of a period of from about 2 to about 4 hours in a vacuum or an atmospheric tumbler. Such tumblers are conventional in the art. Treatment of the meat in this manner has the effect of rendering the muscle sheathes therein less resistant to penetration by the nitrite and DNFH, thereby enhancing dispersion of the latter.
After injection of low-nitrite composition, the meat is subjected to a step of physical treatment such as kneading, tumbling or massaging to facilitate dispersion of the pigment evenly throughout the meat. The step of physical treatment may, for example, utilize a vacuum or atmospheric rotary tumbler for a period of from about 9 to about 18 hours at a rotational speed of from about 10 to about 15 rpm. Those of skill in the art will recognize that types of physical treatment may be used to achieve substantially the same effect.
In this manner, a low-nitrite product, with a uniform colour which is virtually indistinguishable from that of a full-nitrite cured product, is obtained.
The invention will be further described with reference to the following Examples, which are provided for illustrative purposes only and should not be used to limit the scope of the invention.
In the Examples, all chemicals used for analytical work were reagent grade and were obtained from major chemical suppliers. Unless otherwise indicated, all parts are parts by weight.
Example 1 - Synthesis and Microencapsulation of DNFH
4 g of hemin was dissolved in 1 litre of 0.04 M NazC03. To this solution was added 0.2% Tween 80TM (ICI Surfactants, Brantford, Ontario).
The resulting mixture was vigorously agitated with a PolytronTM homogenizer for 30 minutes and thereafter transferred to a 3 litre triple-neck glass reactor.
One litre of 0.05 M phosphate buffer (pH 6.5) containing 5 g sodium ascorbate, and 200 ml ethanol containing 3.5 g ascorbyl palmitate were added. The reactor was flushed with nitrogen, and then nitric oxide gas was bubbled through the reactor for 6 minutes at a rate of 135 mL/min to nitrosate the hemin. The reactor was flushed again with nitrogen and the resulting suspension was transferred to a 400 mL centrifuge bottle. After 15 minutes centrifugation at 7000 rpm, the supernatant was removed and the pigment (DNFH) was recovered for microencapsulation.
DNFH was encapsulated in a carbohydrate matrix (2% DNFH, 98%
carbohydrate) by the spray drying technique described in O'Boyle et al., J.
Food Sc., 57(4), 807, 1992.
Examples 2-7 - Production of Low-Nitrite Cured Meat Products Various cured-meat products were prepare according to the formulations of the products are shown in Table 1.
WO 97/07683 ' PCT/CA96/00573 As will be apparent to those of skill in the art, the meat products produced in Examples 2-7 were as follows:
F1~ Meat Product 2 Smoked turkey wiener 3 Smoked pork wiener Cooked turkey bologna.
Cooked chicken bologna 6 Smoked pork sausage 7 Cooked pork ham In the production of wieners (i.e. Examples 2 and 3), all of the ingredients were placed into a Stephan UMC 12TM vacuum cutter (Stephan Machinery Ltd., Columbus, Ohio). The cutter was evacuated to a pressure of < 50 mmHg absolute and operated until the emulsion temperature had reached 8-9°C. The resultant emulsion was then transferred into a Handtman VFSOTM
(Handtman Canada Ltd., Waterloo, Ontario) continuous vacuum stuffer and was stuffed into 28 mm calibre cellulose casings. The stuffed casings were then smoked in a custom-built, computer-controlled, 136 kg (300 1b) capacity SipromacTM smokehouse (Spiromac Inc., St-Germain-De-Grantham, Quebec).
The smoking process included a 5-step program: (i) drying for 20 minutes at 65 °C and 0 % relative humidity; (ii) smoking with natural smoke for 1 hour at 65 ° C and 25 % relative humidity; (iii) smoke elimination for 10 minutes at 65 °C and 0 % relative humidity; (iv) steam cooking at 75 °C
until the product internal temperature reached 69 ° C at 99 % relative humidity; and (v) showering for 10 minutes. The resultant wieners were then chilled, peeled and vacuum packaged.
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x SUBSTITUTE SHEET (RULE 2S) In the production of bologna (i.e. Examples 4 and 5), a meat emulsion was prepared using the procedure outlined in the previous paragraph. The meat emulsion was stuffed into 75 mm calibre moisture proof SupralonTM casings and the products were cooked in a water bath until the internal temperature reached 69°C.
In the production of smoked sausage (Example 6), the meat (pork) was initially ground through a 3 mm plate and then placed into a 20 L vacuum tumbler together with all of the remaining ingredients. The meat was vacuum tumbled at a pressure of < 100 mmHg absolute for 3-4 hours at 11-12 rpm and thereafter stuffed into 29-32 mm calibre hog casings for the smoked sausage and 75 mm calibre fibrous casings for the salami. The stuffed casings were smoked, using the same 5-step procedure described above for the production of wieners (Examples 2 and 3), chilled and vacuum packaged.
The cooked ham product (Example 7) was made using a mixture of two separately processed meat fractions: coarse pieces (chunks) and fine-cut meats.
The coarse pieces, obtained by grinding meat through plate sizes of 9, 12 or mm, were vacuum tumbled at a pressure of < 100 mmHg absolute with the curing ingredients (i.e. Hela Ham Spice, Hela Ham Pickle Unit and Hela Rapid Cure) for 12-16 hours at 8-12 rpm. The fine-cut fraction was processed in the vacuum cutter using the procedure described above in the production of wieners (Examples 2 and 3). The fine-cut fraction was then mixed with the coarse pieces in the tumbler and the mixture was tumbled for another 0.5-1.5 hours at 12 rpm. The mixture was then stuffed into 90 mm calibre moisture-proof SupralonTM casings. The ham was cooked in a water bath until it reached an internal temperature of 69°C.
Moisture of each of the meat products was determined by drying the meat product to constant weight at 110°C in a forced air oven in accordance with the method described in "Approved Methods of the American Association of Cereal Chemists", 7th Edition, American Association of Cereal Chemists, St.
Paul, 1976, Method 44-15A.
Fat content of each of the meat products was measured by the Soxhlet method described in "Official Methods of the Association of Official Analytical Chemists", 12th Edition, Washington D.C., 1975, Methods 14.035 and 14.036.
Protein content of each of the meat products was recorded as Nx6.25 as determined by the Kjeldahl method, using a BiichiTM Model 425 digester and a Buchi Model 320 distillation unit (Biichi Laboratoriums-Technik AG., Flawil, Switzerland) in accordance with the method described in "Approved Methods of the American Association of Cereal Chemists", 7th Edition, American Association of Cereal Chemists, St. Paul, 1976, Method 46-12.
Moisture content, fat content and protein content for each of the meat products produced in these Examples are provided in Table 2. The results reported are an average of three determinations on one sample for Examples 3, 5, 6 and 7, and for more than one sample for Examples 2 and 4. Also provided in Table 2, for comparative purposes, is moisture content, fat content and protein content for various raw meats.
As shown in Table 2, raw chicken had a higher moisture content compared to the other meat types. However, the moisture content of the final products was also dependent on the type of product, and the formulations.
Proximate compositions of the same product may vary considerably, since each individual batch is necessarily different due to various batches of raw materials.
As expected, the smoked meat products (Examples 2, 3 and 6) lost more moisture than the cooked meat products (Examples 4, 5 and 7), due to use of heat treatment in the smoke house and water-permeable casings in the product of the former.
Examples 8-21 - Production of Low-Nitrite and Full-Nitrite Cured Meat Products In these Examples a number meat products were produced with using various nitrite and pigment levels. Generally, Examples 8-12 illustrate the production of smoked turkey wieners using the formulation and methodology of Example 2 (excluding encapsulated DNFH ingredient); Examples 13-18 illustrate the production of smoked pork wieners using the formulation and methodology of Example 3 (excluding encapsulated DNFH ingredient); and Examples 19-21 illustrate the production of smoked pork sausage using the formulation and methodology of Example 6 (excluding encapsulated DNFH
ingredient).
Sample Moisture Fat Protein Example 2 59.3 (t3.7)15.6 (f3.9) I6.0 (t2.5) Example 4 68.2 (t2.7'8.8 (t3.6) 16.3 (t1.0) Raw turkey breast 71.2 ( f 3.7 ( t0.7) 20.2 ( t 1.5) 2.1) Raw turkey fat 12.5 ( t 85.3 ( t0.8) -1.3) Raw turkey skin 12. 7 ( 75 .1 ( ~ -t 0.9) 1.1 ) Example 3 49. 8 ( 27.8 ( t 2.2)15 .7 ( t t I .9) 0.4) Example 6 64.9 (t1.6)10.3 (t0.6) I4.9 (t0.3) Example 7 79.2 ( ~ 0.6( 10.04) 11.8 ( t0.4) 1.4) Raw pork shoulder 64.4 ( t0.4)16.1 ( t 1.3)17.0 ( t0.5) Raw pork shank 64.0 (t0.5)9.2 (t0.5) 20.8 (t0.8) Example 5 70.4 ( t 7 . 8 ( ~ 15 .2 ( f 0.5) 0.2) 0.4) Raw chicken thigh 71.8 (~0.7)7.3 (f0.4) I7.5 (~0.6) The Hunter colour value for each meat product was determined using a LabScan 6000''"' reflectance-spectrophotometer. The optical sensor used 0°
incident light which was filtered to closely approximate CIE illuminant D65.
Viewing geometry was at 45° through a ring of 16 fibre optic receptor stations.
The spectral data was converted into the standard Hunter L, a, b scale. See, for example, R.S. Hunter & R.W. Harold, "The measurement of Appearance", John Wiley &. Sons Inc., New York, N.Y., 1987.
Hue and chroma were calculated from the "a" and "b" values (hue = arctan (b/a), chroma = aZ+bz)'~2). The results are reported in Table 3 which also includes the nitrite and pigment levels present in the formulation used to produce each meat product.
As shown in Table 3, Example 13, the pork full-nitrite (200 mg/kg) meat product, was significantly more pink (lower hue value), and therefore more preferable, than Example 8, the turkey full-nitrite (200 mg/kg) meat product which was paler looking. Not surprisingly, the nitrite-free products were darker in colour than the full-nitrite parallels ("L" values) due to their different modes of action. However, the low-nitrite meat products (Examples 12, 16-18 and 21), e.g. those containing only 2-4 mg/kg sodium nitrite (1-2%
of the generally accepted level), were characterized by a virtually identical colour when compared to the full-nitrite meat products (Examples 8, 13 and 19).
Example 14 illustrates that use of low-nitrite without pigment is insufficient to produce acceptable colour, and microbial and oxidative stability (see below). In contrast, the combination of low-nitrite with a pigment, such as DNFH, is sufficient to boost the performance of the curing system in a synergistic manner. It is believed that the small amount of nitrite reduces the concentration of metmyochromogen and thus, the intensity of the brownish background.
Table 3 shows that in the case of turkey wieners, the use of 2 mg/kg sodium nitrite in combination with 30 mg/kg DNFH (Example 12) produced almost identical colour to the full-nitrite meat product (Example 8). In the case of smoked pork wieners, the use of 4 mg/kg sodium nitrite in combination with the pigment (Example 16) produced a colour very favourable to that of the full-nitrite meat product (Example 13). Finally, in the case of the smoked pork 0o O W N t~ N et et N N Os N
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SUBSTITUTE SHEET (RULE 26) WO 97/07683 - PCT/C.~96/00573 sausage meat product, the use of 1 mg/kg sodium nitrite in combination with the pigment produced a colour which was improved marginally over the nitrite-free meat product (Example 20).
The extent of lipid oxidation for each meat product was determined by the 2-thiobarbituric acid (TBA) test (TBA number: mg of malondialdehyde equivalent/1000 g meat), using the method according to Tarladgis et al. (J.
Am.
Oil Chem. Soc. 37, 44-48, 1960), as modified by Shahidi et al.(Can. Inst. Food Sci. Technol. J., 20(2), 104-106, 1987), the contents of each of which are hereby incorporated by reference. The samples were vacuum packaged and stored at 4°C. Oxidative stability of the nitrite-free smoked turkey wieners (Examples 8-12) and smoked pork wieners (Examples 13-18) was compared to that of a full-nitrite control product and a blank product containing seasoning but no additives. TBA values were assessed over a 5 week period and yielded the following results: for full-nitrite containing meat product TBA values varied from 0.4 to 0.5 whereas TBA values were 0.9-1.0 for the blank and a steady 0.7 for the nitrite-free wieners. These results indicate that lipid oxidation was almost completely prevented in the case of both full-nitrite and nitrite-free products. Although high initial lipid oxidation values were observed with the nitrite-free products, these values did not increase with time, indicating that the wieners were stable. The mechanical disruption of meat during processing with the lack of nitrite produces the higher initial values, which indicates that the antioxidant strength of the nitrite-free system is somewhat weaker than that of a full-nitrite curing system. However, the nitrite-free curing system is capable of conserving the oxidative state achieved after processing.
Microbial tests were carried out on various of the meat products seven weeks after production using conventional plate count measurement techniques.
The microbial stability of the low nitrite meat products (i.e. Examples 11, 12, 16-18 and 21) compared favourably with that of the full-nitrite containing meat products (i.e. Examples 8, 13 and 19).
WO 97/07683 ~ PCT/CA96/00573 As discussed above, in full-nitrite cured meat products, the residual nitrite is believed to be responsible for the formation of the carcinogenic nitrosamines. Generally, the myoglobin content in meat is in the range of from 0.06 to 2.0 weight percent. To produce a full-nitrite cured meat product having , all the benefits of nitrite, it would thus be necessary to nitrite in an amount of at least 80 mg/kg. In cohtrast, particularly preferred low-nitrite compositions in accordance with the present invention comprise nitrite in an amount in the range of from about 2 to about 10 mg/kg. Thus, low-nitrite composition of the present invention comprises nitrite in an amount less than that conventionally used to cure meat.
Residual nitrite content of the various meat products was measured in accordance with the method described in "Official methods of the Association of Official Analytical Chemists", 14th Edition, Washington D.C., 1984, Method 24.044. The results are reported in Table 4. As shown in Table 4, there was no detectable residual nitrite in both the nitrite-free (Examples 10, 15 and 20) and the low-nitrite (Examples 11, 16 and 21) meat products. In contrast, the full-nitrite (Examples 8, 13 and 19) meat products were characterized by significant levels of residual nitrites giving rise to an increased potential for the formation of nitrosamines.
Example Nitrite (mg/kg)DNFH (mg/kg) Residual Nitrite (mg/kg) 8 200 0 52.4 10 0 30 not detectable 11 10 30 not detectable 13 200 0 60.8 15 0 30 not detectable 16 4 30 not detectable 19 200 0 20.0 20 0 30 not detectable 21 1 30 not detectable
The resulting mixture was vigorously agitated with a PolytronTM homogenizer for 30 minutes and thereafter transferred to a 3 litre triple-neck glass reactor.
One litre of 0.05 M phosphate buffer (pH 6.5) containing 5 g sodium ascorbate, and 200 ml ethanol containing 3.5 g ascorbyl palmitate were added. The reactor was flushed with nitrogen, and then nitric oxide gas was bubbled through the reactor for 6 minutes at a rate of 135 mL/min to nitrosate the hemin. The reactor was flushed again with nitrogen and the resulting suspension was transferred to a 400 mL centrifuge bottle. After 15 minutes centrifugation at 7000 rpm, the supernatant was removed and the pigment (DNFH) was recovered for microencapsulation.
DNFH was encapsulated in a carbohydrate matrix (2% DNFH, 98%
carbohydrate) by the spray drying technique described in O'Boyle et al., J.
Food Sc., 57(4), 807, 1992.
Examples 2-7 - Production of Low-Nitrite Cured Meat Products Various cured-meat products were prepare according to the formulations of the products are shown in Table 1.
WO 97/07683 ' PCT/CA96/00573 As will be apparent to those of skill in the art, the meat products produced in Examples 2-7 were as follows:
F1~ Meat Product 2 Smoked turkey wiener 3 Smoked pork wiener Cooked turkey bologna.
Cooked chicken bologna 6 Smoked pork sausage 7 Cooked pork ham In the production of wieners (i.e. Examples 2 and 3), all of the ingredients were placed into a Stephan UMC 12TM vacuum cutter (Stephan Machinery Ltd., Columbus, Ohio). The cutter was evacuated to a pressure of < 50 mmHg absolute and operated until the emulsion temperature had reached 8-9°C. The resultant emulsion was then transferred into a Handtman VFSOTM
(Handtman Canada Ltd., Waterloo, Ontario) continuous vacuum stuffer and was stuffed into 28 mm calibre cellulose casings. The stuffed casings were then smoked in a custom-built, computer-controlled, 136 kg (300 1b) capacity SipromacTM smokehouse (Spiromac Inc., St-Germain-De-Grantham, Quebec).
The smoking process included a 5-step program: (i) drying for 20 minutes at 65 °C and 0 % relative humidity; (ii) smoking with natural smoke for 1 hour at 65 ° C and 25 % relative humidity; (iii) smoke elimination for 10 minutes at 65 °C and 0 % relative humidity; (iv) steam cooking at 75 °C
until the product internal temperature reached 69 ° C at 99 % relative humidity; and (v) showering for 10 minutes. The resultant wieners were then chilled, peeled and vacuum packaged.
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~ x ~ g ~ . a .O.N aUnx m . . ~ a a H ~ a i ~ x x o.
0 U ,x :: ~ ~ ~ . ~ ' 0 ~
= . U n ~ ~ ~ " ,~ '~ 0 3 x x x ' ~ ~ w ~ H
x SUBSTITUTE SHEET (RULE 2S) In the production of bologna (i.e. Examples 4 and 5), a meat emulsion was prepared using the procedure outlined in the previous paragraph. The meat emulsion was stuffed into 75 mm calibre moisture proof SupralonTM casings and the products were cooked in a water bath until the internal temperature reached 69°C.
In the production of smoked sausage (Example 6), the meat (pork) was initially ground through a 3 mm plate and then placed into a 20 L vacuum tumbler together with all of the remaining ingredients. The meat was vacuum tumbled at a pressure of < 100 mmHg absolute for 3-4 hours at 11-12 rpm and thereafter stuffed into 29-32 mm calibre hog casings for the smoked sausage and 75 mm calibre fibrous casings for the salami. The stuffed casings were smoked, using the same 5-step procedure described above for the production of wieners (Examples 2 and 3), chilled and vacuum packaged.
The cooked ham product (Example 7) was made using a mixture of two separately processed meat fractions: coarse pieces (chunks) and fine-cut meats.
The coarse pieces, obtained by grinding meat through plate sizes of 9, 12 or mm, were vacuum tumbled at a pressure of < 100 mmHg absolute with the curing ingredients (i.e. Hela Ham Spice, Hela Ham Pickle Unit and Hela Rapid Cure) for 12-16 hours at 8-12 rpm. The fine-cut fraction was processed in the vacuum cutter using the procedure described above in the production of wieners (Examples 2 and 3). The fine-cut fraction was then mixed with the coarse pieces in the tumbler and the mixture was tumbled for another 0.5-1.5 hours at 12 rpm. The mixture was then stuffed into 90 mm calibre moisture-proof SupralonTM casings. The ham was cooked in a water bath until it reached an internal temperature of 69°C.
Moisture of each of the meat products was determined by drying the meat product to constant weight at 110°C in a forced air oven in accordance with the method described in "Approved Methods of the American Association of Cereal Chemists", 7th Edition, American Association of Cereal Chemists, St.
Paul, 1976, Method 44-15A.
Fat content of each of the meat products was measured by the Soxhlet method described in "Official Methods of the Association of Official Analytical Chemists", 12th Edition, Washington D.C., 1975, Methods 14.035 and 14.036.
Protein content of each of the meat products was recorded as Nx6.25 as determined by the Kjeldahl method, using a BiichiTM Model 425 digester and a Buchi Model 320 distillation unit (Biichi Laboratoriums-Technik AG., Flawil, Switzerland) in accordance with the method described in "Approved Methods of the American Association of Cereal Chemists", 7th Edition, American Association of Cereal Chemists, St. Paul, 1976, Method 46-12.
Moisture content, fat content and protein content for each of the meat products produced in these Examples are provided in Table 2. The results reported are an average of three determinations on one sample for Examples 3, 5, 6 and 7, and for more than one sample for Examples 2 and 4. Also provided in Table 2, for comparative purposes, is moisture content, fat content and protein content for various raw meats.
As shown in Table 2, raw chicken had a higher moisture content compared to the other meat types. However, the moisture content of the final products was also dependent on the type of product, and the formulations.
Proximate compositions of the same product may vary considerably, since each individual batch is necessarily different due to various batches of raw materials.
As expected, the smoked meat products (Examples 2, 3 and 6) lost more moisture than the cooked meat products (Examples 4, 5 and 7), due to use of heat treatment in the smoke house and water-permeable casings in the product of the former.
Examples 8-21 - Production of Low-Nitrite and Full-Nitrite Cured Meat Products In these Examples a number meat products were produced with using various nitrite and pigment levels. Generally, Examples 8-12 illustrate the production of smoked turkey wieners using the formulation and methodology of Example 2 (excluding encapsulated DNFH ingredient); Examples 13-18 illustrate the production of smoked pork wieners using the formulation and methodology of Example 3 (excluding encapsulated DNFH ingredient); and Examples 19-21 illustrate the production of smoked pork sausage using the formulation and methodology of Example 6 (excluding encapsulated DNFH
ingredient).
Sample Moisture Fat Protein Example 2 59.3 (t3.7)15.6 (f3.9) I6.0 (t2.5) Example 4 68.2 (t2.7'8.8 (t3.6) 16.3 (t1.0) Raw turkey breast 71.2 ( f 3.7 ( t0.7) 20.2 ( t 1.5) 2.1) Raw turkey fat 12.5 ( t 85.3 ( t0.8) -1.3) Raw turkey skin 12. 7 ( 75 .1 ( ~ -t 0.9) 1.1 ) Example 3 49. 8 ( 27.8 ( t 2.2)15 .7 ( t t I .9) 0.4) Example 6 64.9 (t1.6)10.3 (t0.6) I4.9 (t0.3) Example 7 79.2 ( ~ 0.6( 10.04) 11.8 ( t0.4) 1.4) Raw pork shoulder 64.4 ( t0.4)16.1 ( t 1.3)17.0 ( t0.5) Raw pork shank 64.0 (t0.5)9.2 (t0.5) 20.8 (t0.8) Example 5 70.4 ( t 7 . 8 ( ~ 15 .2 ( f 0.5) 0.2) 0.4) Raw chicken thigh 71.8 (~0.7)7.3 (f0.4) I7.5 (~0.6) The Hunter colour value for each meat product was determined using a LabScan 6000''"' reflectance-spectrophotometer. The optical sensor used 0°
incident light which was filtered to closely approximate CIE illuminant D65.
Viewing geometry was at 45° through a ring of 16 fibre optic receptor stations.
The spectral data was converted into the standard Hunter L, a, b scale. See, for example, R.S. Hunter & R.W. Harold, "The measurement of Appearance", John Wiley &. Sons Inc., New York, N.Y., 1987.
Hue and chroma were calculated from the "a" and "b" values (hue = arctan (b/a), chroma = aZ+bz)'~2). The results are reported in Table 3 which also includes the nitrite and pigment levels present in the formulation used to produce each meat product.
As shown in Table 3, Example 13, the pork full-nitrite (200 mg/kg) meat product, was significantly more pink (lower hue value), and therefore more preferable, than Example 8, the turkey full-nitrite (200 mg/kg) meat product which was paler looking. Not surprisingly, the nitrite-free products were darker in colour than the full-nitrite parallels ("L" values) due to their different modes of action. However, the low-nitrite meat products (Examples 12, 16-18 and 21), e.g. those containing only 2-4 mg/kg sodium nitrite (1-2%
of the generally accepted level), were characterized by a virtually identical colour when compared to the full-nitrite meat products (Examples 8, 13 and 19).
Example 14 illustrates that use of low-nitrite without pigment is insufficient to produce acceptable colour, and microbial and oxidative stability (see below). In contrast, the combination of low-nitrite with a pigment, such as DNFH, is sufficient to boost the performance of the curing system in a synergistic manner. It is believed that the small amount of nitrite reduces the concentration of metmyochromogen and thus, the intensity of the brownish background.
Table 3 shows that in the case of turkey wieners, the use of 2 mg/kg sodium nitrite in combination with 30 mg/kg DNFH (Example 12) produced almost identical colour to the full-nitrite meat product (Example 8). In the case of smoked pork wieners, the use of 4 mg/kg sodium nitrite in combination with the pigment (Example 16) produced a colour very favourable to that of the full-nitrite meat product (Example 13). Finally, in the case of the smoked pork 0o O W N t~ N et et N N Os N
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SUBSTITUTE SHEET (RULE 26) WO 97/07683 - PCT/C.~96/00573 sausage meat product, the use of 1 mg/kg sodium nitrite in combination with the pigment produced a colour which was improved marginally over the nitrite-free meat product (Example 20).
The extent of lipid oxidation for each meat product was determined by the 2-thiobarbituric acid (TBA) test (TBA number: mg of malondialdehyde equivalent/1000 g meat), using the method according to Tarladgis et al. (J.
Am.
Oil Chem. Soc. 37, 44-48, 1960), as modified by Shahidi et al.(Can. Inst. Food Sci. Technol. J., 20(2), 104-106, 1987), the contents of each of which are hereby incorporated by reference. The samples were vacuum packaged and stored at 4°C. Oxidative stability of the nitrite-free smoked turkey wieners (Examples 8-12) and smoked pork wieners (Examples 13-18) was compared to that of a full-nitrite control product and a blank product containing seasoning but no additives. TBA values were assessed over a 5 week period and yielded the following results: for full-nitrite containing meat product TBA values varied from 0.4 to 0.5 whereas TBA values were 0.9-1.0 for the blank and a steady 0.7 for the nitrite-free wieners. These results indicate that lipid oxidation was almost completely prevented in the case of both full-nitrite and nitrite-free products. Although high initial lipid oxidation values were observed with the nitrite-free products, these values did not increase with time, indicating that the wieners were stable. The mechanical disruption of meat during processing with the lack of nitrite produces the higher initial values, which indicates that the antioxidant strength of the nitrite-free system is somewhat weaker than that of a full-nitrite curing system. However, the nitrite-free curing system is capable of conserving the oxidative state achieved after processing.
Microbial tests were carried out on various of the meat products seven weeks after production using conventional plate count measurement techniques.
The microbial stability of the low nitrite meat products (i.e. Examples 11, 12, 16-18 and 21) compared favourably with that of the full-nitrite containing meat products (i.e. Examples 8, 13 and 19).
WO 97/07683 ~ PCT/CA96/00573 As discussed above, in full-nitrite cured meat products, the residual nitrite is believed to be responsible for the formation of the carcinogenic nitrosamines. Generally, the myoglobin content in meat is in the range of from 0.06 to 2.0 weight percent. To produce a full-nitrite cured meat product having , all the benefits of nitrite, it would thus be necessary to nitrite in an amount of at least 80 mg/kg. In cohtrast, particularly preferred low-nitrite compositions in accordance with the present invention comprise nitrite in an amount in the range of from about 2 to about 10 mg/kg. Thus, low-nitrite composition of the present invention comprises nitrite in an amount less than that conventionally used to cure meat.
Residual nitrite content of the various meat products was measured in accordance with the method described in "Official methods of the Association of Official Analytical Chemists", 14th Edition, Washington D.C., 1984, Method 24.044. The results are reported in Table 4. As shown in Table 4, there was no detectable residual nitrite in both the nitrite-free (Examples 10, 15 and 20) and the low-nitrite (Examples 11, 16 and 21) meat products. In contrast, the full-nitrite (Examples 8, 13 and 19) meat products were characterized by significant levels of residual nitrites giving rise to an increased potential for the formation of nitrosamines.
Example Nitrite (mg/kg)DNFH (mg/kg) Residual Nitrite (mg/kg) 8 200 0 52.4 10 0 30 not detectable 11 10 30 not detectable 13 200 0 60.8 15 0 30 not detectable 16 4 30 not detectable 19 200 0 20.0 20 0 30 not detectable 21 1 30 not detectable
Claims (22)
1. A low-nitrite composition for curing meat comprising: (i) a nitrite, (ii) a pigment and (iii) an antioxidant, the nitrite being present in an amount of from about 2 to about 10 milligrams per kilogram of meat to be cured.
2. The composition defined in claim 1, wherein the pigment is selected from the group consisting essentially of dinitrosyl ferrohemochrome, beet pigment and mixtures thereof.
3. The composition defined in claim 1, wherein the pigment is dinitrosyl ferrohemochrome.
4. The composition defined in claim 1, further comprising (iv) at least one sequestering agent.
5. The composition defined in claim 1, further comprising: (V) at least one antimicrobial agent.
6. The composition defined in claim 3, wherein the dinitrosyl ferrohemochrome is present in an amount of from about 10 to about 60 milligrams per kilogram of meat to be cured.
7. The composition defined in claim 3, wherein the dinitrosyl ferrohemochrome is encapsulated in an edible polymer film.
8. The composition defined in claim 7, wherein the edible polymer film is a carbohydrate film.
9. The composition defined in claim 1, wherein the antioxidant agent comprises at least one member selected from the group consisting essentially of ascorbic acid, sodium ascorbate, ascorbyl palmitate, erythorbic acid, ascorbyl acetal, butylated hydroxy anisole, butylaled hydroxytoluene, t-butylhydroquinone, d,l-alpha-tocopherol, propyl gallate, nordihydroguaiaretic acid, lecithin, dilauryl thiodiproprionate, deflavourized rosemary spice extract and mixtures thereof.
10. The composition defined in claim 5, wherein the antimicrobial agent comprises at least one member selected from the group consisting essentially of sodium hypophosphite, potassium sorbate, lactic acid-producing bacteria, sodium lactate, 3-(4-tolyl sulfonyl)acrylonitrile, nisin, propylparahydroxybenzoate, methyl fumarate, dimethyl fumarate, ethyl fumarate, diethylfumate and mixtures thereof.
11. The composition defined in claim 4, wherein the sequestering agent comprises at least one member selected from the group consisting essentially of sodium hypophosphite, monosodium phosphate, disodium phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium citrate, citric acid, monoglyceride citrate, 8-hydroxyquinoline, sodium gluconate, catechol, ethylenediamine tetraacetic acid, disodium ethylenediamine tetracetate, diethylenetriamine pentaacetic acid and salicylic acid.
12. A process for preparing a low-nitrite cured meat product comprising the steps of:
(i) adding to a meat product an effective amount of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant, the nitrite being present in the meat curing composition in an amount of from about 2 to about 10 milligrams per kilogram of meat to be cured;
(ii) distributing the meat curing composition substantially evenly throughout the meat product; and (iii) processing the meat product having the meat curing composition distributed therein.
(i) adding to a meat product an effective amount of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant, the nitrite being present in the meat curing composition in an amount of from about 2 to about 10 milligrams per kilogram of meat to be cured;
(ii) distributing the meat curing composition substantially evenly throughout the meat product; and (iii) processing the meat product having the meat curing composition distributed therein.
13. The process defined in claim 12, wherein the meat product is a comminuted meat emulsion.
14. The process defined in claim 12, wherein the distribution of pigment takes place under substantially oxygen free conditions.
15. The process defined in claim 12, wherein the pigment is dinitrosyl ferrohemochrome.
16. The process defined in claim 12, wherein the composition further comprises at least one sequestering agent.
17. The process defined in claim 15, wherein the dinitrosyl ferrohemochrome is present in the meat curing composition in an amount of from about 10 to about 60 milligrams per kilogram of meat to be cured.
18. A process for preparing low-nitrite cured solid meat product comprising the steps of (i) preparing a dispersion of a low-nitrite meat curing composition comprising an effective amount of a nitrite, a pigment and an antioxidant, the nitrite being present in the meat curing composition in amount of from about 2 to about 10 milligrams per kilogram of meat to be cured;
(ii) injecting the dispersion into a solid meat product; and (iii) physically treating the solid meat product;
(iv) processing the solid meat product having the meat curing composition distributed therein.
(ii) injecting the dispersion into a solid meat product; and (iii) physically treating the solid meat product;
(iv) processing the solid meat product having the meat curing composition distributed therein.
19. The process defined in claim 18, further comprising the step of physically treating the solid meat product by tumbling or massaging prior to injecting the dispersion therein.
20. The process defined in claim 18, wherein the pigment is dinitrosyl ferrohemochrome.
21. The process defined in claim 18, wherein the composition further comprises at least one sequestering agent.
22. The process defined in claim 20, wherein the dinitrosyl ferrohemochrome is present in the meat curing composition in an amount of from about 10 to about 60 milligrams per kilogram of meat to be cured.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51956595A | 1995-08-25 | 1995-08-25 | |
| US08/519,565 | 1995-08-25 | ||
| PCT/CA1996/000573 WO1997007683A1 (en) | 1995-08-25 | 1996-08-26 | Low-nitrite composition for curing meat and process for preparing low-nitrite cured meat products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2230504A1 CA2230504A1 (en) | 1997-03-06 |
| CA2230504C true CA2230504C (en) | 2007-02-20 |
Family
ID=24068854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002230504A Expired - Fee Related CA2230504C (en) | 1995-08-25 | 1996-08-26 | Low-nitrite composition for curing meat and process for preparing low-nitrite cured meat products |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU6729496A (en) |
| CA (1) | CA2230504C (en) |
| WO (1) | WO1997007683A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112869045A (en) * | 2021-01-22 | 2021-06-01 | 中盐金坛盐化有限责任公司 | Salted meat salt and preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2147261A (en) * | 1936-05-23 | 1939-02-14 | Corn Ind Res Foundation | Producing stable color in meats |
| US2831774A (en) * | 1954-12-17 | 1958-04-22 | Armour & Co | Process for the improvement of color in meat |
| US2901354A (en) * | 1955-08-18 | 1959-08-25 | Cudahy Packing Company | Method of protecting dry sausage against discoloration and rancidity |
| NZ180952A (en) * | 1975-06-09 | 1979-10-25 | Mayer & Co Inc O | Precooked sliced bacon |
| DE2528750A1 (en) * | 1975-06-27 | 1977-01-20 | Wenzel Siegfried | Lowering residual nitrite concn. in meat products - using haemoglobin |
| US4543260A (en) * | 1979-10-26 | 1985-09-24 | Stauffer Chemical Company | Process for curing bacon, product thereof and composition therefor |
| US4559234A (en) * | 1984-05-30 | 1985-12-17 | Canadian Patents And Development Limited | Meat curing compositions and method of use |
| CA2023966C (en) * | 1990-08-24 | 2004-03-23 | Leon J. Rubin | Nitrite-free meat curative and process of curing meat |
| JPH06237737A (en) * | 1993-02-16 | 1994-08-30 | Snow Brand Food Co Ltd | Ingredient for meat product, its production and meat product |
-
1996
- 1996-08-26 CA CA002230504A patent/CA2230504C/en not_active Expired - Fee Related
- 1996-08-26 AU AU67294/96A patent/AU6729496A/en not_active Abandoned
- 1996-08-26 WO PCT/CA1996/000573 patent/WO1997007683A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| AU6729496A (en) | 1997-03-19 |
| WO1997007683A1 (en) | 1997-03-06 |
| CA2230504A1 (en) | 1997-03-06 |
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