Patent Application
20240301167
The present disclosure relates generally to a method of obtaining volatile or semi-volatile natural antioxidants from comestible byproducts and, in particular, toasted comestible byproducts, to the natural antioxidants obtained therefrom, and to packaging films incorporating such natural antioxidants.
Butylated hydroxytoluene (BHT) is a synthetically produced compound commonly used as an antioxidant and preservative. BHT is often incorporated into food packaging by impregnating the BHT into plastic liners or film used to make the food packaging. In use, the BHT migrates out of the packaging over time to interact with the food and helps prevent spoilage of the food. Other synthetically produced antioxidants, such as tert-butylhydroquinone (TBHQ) or butylated hydroxyanisole (BHA) are sometimes used in place of BHT in a similar manner.
TBHQ, BHA, and BHT are synthetic chemicals and becoming less desired by consumers. Consumers have shown a growing preference for more natural preservatives, rather than synthetically produced compounds. However, using natural preservatives and antioxidants in place of BHT, BHA, and TBHQ present challenges. Attempts have been made, for example, to use mixed tocopherols and/or rosemary extract in place of the BHT, BHA, or TBHQ. However, these options are more expensive and do not function as an antioxidant as well as BHT, BHA, or TBHQ. Mixed tocopherols and rosemary extract are also not volatile or even semi-volatile and, thus, need to be applied directly to foods rather than impregnated in packaging in order to function as antioxidants. Because these alternative antioxidants need to be applied directly to the foods, they may degrade due to the application method and/or subsequent processing of the food (such as cooking under pressure, heating, drying, etc.) Rosemary extract may also impart unwanted flavors and/or aromas to the foods it is attempting to protect. Thus, current natural alternatives to BHT, BHA, and TBHQ exhibit several shortcomings.
In one aspect, a method of obtaining a volatile or semi-volatile natural antioxidant from a comestible byproduct is provided. In some embodiments or approaches, the methods include providing a comestible byproduct having a source of phenolic compounds and optionally grinding the comestible byproduct. The method further incudes toasting the comestible byproduct or optionally ground comestible byproduct for a time and at a temperature effective to volatilize and thermally convert the phenolic compounds of the comestible byproduct or the optionally ground comestible byproduct into volatilized compounds including one or more substituted phenolic compounds, and recovering the volatilized compounds including the one or more substituted phenolic compounds for use as the volatile or semi-volatile natural antioxidant.
In other aspects, the method of the previous paragraph may be combined with one or more optional features individually or in any combinations thereof. These optional features include one or more of the following: wherein the comestible byproduct is selected from canola meal, wheat bran, pomace, straw, coffee fruit, green coffee bean, roasted coffee beans, roast and ground coffee, spent coffee grounds, and combinations thereof; and/or wherein the toasting includes dry heating at atmospheric pressure for about 10 minutes to about 20 minutes at about 165° C. to about 250° C., optionally under an inert gas purge; and/or wherein the recovering includes cold trapping of the volatilized compounds; and/or further comprising incorporating the recovered volatilized compounding including the one or more substituted phenolic compounds into a polymer substrate for use as packaging material; and/or wherein the polymer substrate is selected form polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA), polypropylene, polylactic acid (PLA), metalocene, polybutylene, and mixtures thereof; and/or wherein the one or more substituted phenolic compounds include one or more substituted methoxy phenol compounds; and/or wherein the one or more substituted phenolic compounds include a 4,6-subustituted 2-methoxy phenol or derivative thereof; and/or wherein the 4,6-substitution is selected from hydrogen, a methoxy group, a methyl group, a vinyl group, and combinations thereof; and/or wherein the volatile or semi-volatile antioxidant has a vapor pressure from about 0.0005 mm to about 0.5 mm of Hg at about 25° C.
In yet further aspects, a packaging film including a volatile or semi-volatile natural antioxidant sourced from a toasted comestible byproduct is provided. The packaging film may include a flexible packaging film having an amount of a natural antioxidant sourced from a toasted comestible byproduct. In one approach, the natural antioxidant may be any of the antioxidants as described in the previous two paragraphs. In other approaches, the natural antioxidant may include a 4,6-substituted 2-methoxy phenol or derivative thereof.
In yet further aspects, the packaging film of the previous paragraph may be combined with one or more optional features either individually or in any combination. These optional features include one or more of the following: wherein the 4,6-substitution is selected from hydrogen, a methoxy group, a methyl group, a vinyl group, and combinations thereof; and/or wherein the natural antioxidant is selected from 2-methoxy-4-methylphenol, 2-methoxyphenol, 2,6-dimethoxyl-4-vinylphenol, substituted vinyl phenols, derivatives thereof, and combinations thereof; and/or wherein the natural antioxidant is obtained from toasting a phenolic-acid and/or polyphenolic containing comestible byproduct; and/or wherein the polyphenolic and/or phenolic-acid containing comestible byproduct is selected from canola meal, wheat bran, pomace, straw, coffee, coffee beans, coffee fruit, roast and ground coffee, spent coffee grounds, and combinations thereof; and/or wherein the toasting includes dry heating at atmospheric pressure for about 10 minutes to about 20 minutes at about 165° C. to about 250° C., optionally under an inert gas purge; and/or wherein the flexible packaging film includes polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA), polypropylene, polylactic acid (PLA), metalocene, polybutylene, and mixtures thereof; and/or wherein the flexible packaging film is a multi-layer film and wherein one of the layers includes the amount of the natural antioxidant; and/or wherein another of the layers in the multi-layer film is a barrier layer selected from high density polyethylene (HDPE), polyvinylidene chloride (PVDC), ethylene-vinyl alcohol copolymer (EVOH), and combinations thereof; and/or wherein the amount of the natural antioxidant in the packaging film limits the amount of hexanal formation from a food source prone to oxidation to less than about 3 ppm after 12 weeks of storage at about 90° F. to about 101° F.
In another aspect, a volatile or semi-volatile natural antioxidant obtained from a toasted comestible byproduct is provided herein. The volatile or semi-volatile natural antioxidant may include a compound of Formula I:
wherein R1 and R2 are independently selected from a hydrogen, an alkoxy group, an alkyl group having C1 to C6 carbon atoms, and a C1 to C6 hydrocarbyl group including one or more vinyl carbons therein (in other approaches, a C1 to C4 carbon group or C2 to C4 hydrocarbyl group). Any of the previously described aspects may also include the natural antioxidant of Formula I as described in this paragraph or the following paragraph.
The volatile or semi-volatile natural antioxidant of the previous paragraph may also be combined with one or more optional features either individually or in any combination thereof. These optional features include one or more of the following: wherein the volatile or semi-volatile natural antioxidant has a vapor pressure of about 0.0005 mm Hg at 25° C. to about 0.5 mm Hg at 25° C.; wherein R1 is hydrogen and R2 is a methyl group; wherein R1 is a methoxy group and R2 is a C2 vinyl group; wherein R1 is hydrogen and R2 is a C2 vinyl group; and/or wherein the compound of Formula I is derived from a toasted phenolic-acid or polyphenolic containing comestible byproduct; and/or wherein the phenolic-acid or polyphenolic containing comestible byproduct is selected from canola meal, wheat bran, pomace, straw, coffee, coffee beans, coffee fruit, roast and ground coffee, spent coffee grounds, and combinations thereof.
The drawings described herein are for illustrative purposes only of selected configurations and not all possible implementations, and are not intended to limit the scope of the present disclosure;
Disclosed herein are methods of obtaining volatile or semi-volatile natural antioxidants from comestible byproducts, the resulting natural antioxidants obtained from the comestible byproducts, and packaging films incorporating such natural antioxidants. In one aspect, the methods described herein provide the volatile or semi-volatile natural antioxidant from a comestible byproduct that includes a source of polyphenolic and/or phenolic acid compounds. The selected comestible byproduct may be heated or toasted to volatilize and convert the polyphenolic and/or phenolic acid compounds of the comestible byproduct into the volatile or semi-volatile natural antioxidants. It is believed that the selected comestible byproducts themselves, however, do not include the compounds providing the antioxidant functionality (or include only small or negligible amounts), but the methods herein include processing conditions and recovery methods to obtain the desired volatile and/or semi-select volatile compounds and convert target compounds therein into those with antioxidant functionality in a quantity sufficient to provide the desired antioxidant effect.
In some aspects, the recovered natural antioxidants herein include one or more substituted phenolic compounds, such as substituted methoxy phenol compounds, and the like, that are volatilized and thermally converted from polyphenolic and/or phenolic acid compounds in the starting comestible byproduct. The methods herein also provide for recovering the volatilized and converted compounds for use as the natural antioxidants. In some approaches, the recovery methods include natural recovery methods devoid of organic solvents and the like so that even after recovery, the antioxidants remain natural.
It was discovered that certain comestible byproduct streams including sources of select polyphenolic and/or phenolic acid compounds could be processed to volatilize and convert the select compounds therein into a material with antioxidant activity similar to and/or better than BHT, BHA, and TBHQ. As discussed herein, and with any embodiment of this disclosure, the methods recover natural antioxidants from the starting comestible byproduct by converting, transforming, and volatilizing the compounds. The converting and volatilizing may occur simultaneously or in any order. That is, the converting and volatilizing may occur at the same time, or the compound may first be converted and volatilized, or vice versa or any combination thereof depending on the starting material and particular compound. It was discovered that by dry heating or toasting the comestible byproduct for an effective time and temperature, certain compounds therein could be volatilized and converted into the new substituted phenolic compound, such as methoxy phenol compounds, that have high antioxidant activity. The volatilized compounds could then be isolated for use as preservatives/antioxidants and used with foods and/or incorporated into food packaging films (e.g., plastic liners) similar to BHT, BHA and TBHQ. A shelf-life study of the naturally-sourced and naturally-produced volatile antioxidants showed that they are effective for preventing rancidity of cereal similar to or better than BHT.
The antioxidants described herein are produced naturally by dry heating or toasting the comestible byproduct, thereby producing volatilized and converted compounds, and thereafter capturing the volatilized compounds (in some cases, using natural capturing methods). The comestible byproduct(s) are selected due to a source of polyphenolic and/or phenolic acid compounds that can easily be converted into the desired antioxidants that are volatilized by the dry heating or toasting process. In some approaches, the comestible byproducts can optionally be ground in order to increase surface area for the heating/toasting process and release of volatilized compounds. The dry heating or toasting process is performed for a time and temperature effective to volatize and thermally convert the polyphenolic and/or phenolic acid compounds of the comestible byproduct into volatilized compounds including, in some approaches, one or more substituted methoxy phenol compounds. The volatilized compounds are recovered for use as antioxidants, which can be incorporated into packaging, such as a food liner.
Turning to more of the specifics, the starting comestible byproduct is a processed comestible or other spent food product that preferably includes a source of polyphenolic and/or phenolic acid compounds. The natural antioxidants herein are derived from sources that would otherwise have little or no practical use and commonly discarded. For example, the comestible byproduct may be selected from (to suggest but a few sources of polyphenolic and/or phenolic acid compounds) canola meal, bran (wheat bran, corn bran, and the like and mixtures thereof) pomace (e.g., olive, grape, and the like and mixtures thereof), straw, green coffee bean, roasted coffee beans, roast and ground coffee, spent coffee grounds, coffee fruit, soybean residue (residue after the oil and protein removal) and combinations thereof. The comestible byproducts can be obtained from wheat milling companies, olive producers, the wine industry, or the canola oil industry to suggest a few sources. The select byproduct(s) are a source of polyphenolic and/or phenolic acid compounds, which, when dry heated or toasted as described herein release volatilized compounds that are also converted into one or more substituted phenol compounds (such as substituted methoxy phenolic compounds as further discussed herein) that are effective as natural antioxidants as discussed further herein. Optionally, the starting comestible byproduct may be ground prior to the heating to increase surface area. Grinding may be through any suitable method to obtain a particle size of about 1 mm to about 3 mm in size using conventional grinding equipment. In some approaches, the concentration of phenolic and polyphenolic compounds in the starting comestible byproduct may be about 20 mg/g GAE to about 2,200 mg/g GAE (gallic acid equivalent), but such levels may vary depending on the starting material source.
The volatilized and converted compounds recovered from the byproduct include one or more volatile or semi-volatile antioxidants and have antioxidant functionality. The volatile or semi-volatile antioxidants derived and converted from the comestible byproducts include at least one or more substituted phenol compounds, such as one or more methoxy phenol compounds, which are believed to contribute significantly to the antioxidant properties of the recovered volatilized compounds.
In some approaches, the one or more methoxy phenol compounds may include 4,6-substituted 2-methoxy phenol or derivatives thereof. The 4,6 substitution may be selected from hydrogen, methoxy, methyl, vinyl and combinations thereof. The one or more methoxy phenol compounds may include, but not limited to, for example, 2-methoxy-4-methylphenol, 2,6-dimethoxy-4-vinylphenol, 2-methoxy-4-vinylphenol, and mixtures thereof. The volatile or semi-volatile antioxidants may also include other volatile or semi-volatile antioxidants in addition to the methoxy phenol compounds herein. The volatile or semi-volatile antioxidants may advantageously have little or no aroma as compared to other natural antioxidants with strong characteristic aroma (such as the prior rosemary extracts, for example). Advantageously, the volatile or semi-volatile natural antioxidants herein have a volatility consistent to BHT, BHA, and TBHQ and, in some approaches, may have a vapor pressure of about 0.0005 mm to about 0.5 mm of Hg at 25° C.
In other approaches or embodiments, the volatile or semi-volatile natural antioxidants obtained from the methods herein and from a dry heated or toasted comestible byproduct include at least a compound of Formula I:
wherein R1 and R2 are independently selected from a hydrogen, an alkoxy group, an alkyl group having C1 to C6 carbon atoms, and a C1 to C6 hydrocarbyl group including one or more vinyl carbons therein. In some embodiments, R1 is hydrogen and R2 is a methyl group. In other embodiments, R1 is a methoxy group and R2 is a C2 vinyl group. And in other embodiments, R1 is hydrogen and R2 is a C2 vinyl group.
The toasting process of the select comestible byproducts herein may include dry heating or toasting the comestible byproduct at atmospheric pressure for about 10 to about 20 minutes at about 165° C. to about 250° C., optionally under an inert gas purge. (In other approaches, for a time ranging from at least about 10 minutes, at least about 12 mins, at least about 14 min, or at least about 16 min to less than about 20 mins, less than about 18 mins, less than about 16 mins, or less than about 14 mins. In other approaches, a temperature ranging from at least about 165° C., at least about 170° C., at least about 180° C., at least about 190° C., or at least about 200°° C. to less than about 250° C., less than about 240° C., less than about 230° C., less than 220° C., or less than about 210° C.) During the dry heating or toasting, it is believed that the comestible byproducts or portions thereof may undergo pyrolysis that thermally degrades non-volatile lignins present in the byproduct materials; thus, producing a range of semi-volatile and volatile substances including those described above.
Recovery of the volatilized and converted compounds released from the dry heating or toasting the byproducts can be performed using natural recovery methods. For example,
The volatile or semi-volatile antioxidants herein may be added to, incorporated with, impregnated, or blended into a polymer substrate for use as a packaging material similar to BHT, BHA, or TBHQ. This can be done in accordance with the known methods for incorporating semi-volatile antioxidants, such as BHT, into polymers and other films commonly used as a packaging material, where the natural volatile or semi-volatile antioxidants herein are configured to migrate out of the polymer, film, or other packaging material and onto the food stored with the packaging material over time similar to BHT. The natural antioxidants described herein are advantageously volatile or semi-volatile to a similar level as BHT, which allows them to be incorporated into the polymer or packaging material and then migrate out of the packaging material and onto food during storage to prevent oxidative rancidity development. In some approaches, about 600 ppm to about 2000 ppm of the natural antioxidant herein (in other approaches, amounts ranging from at least about 700 ppm, at least about 900 ppm, at least about 900 ppm, at least about 1000 ppm, or at least about 1200 ppm to less than about 2000 ppm, less than about 1800 ppm, less than about 1600 ppm, or less than about 1400 ppm) may be provided in conventional packaging films and function to limit the amount of hexanal formation from a food source prone to oxidation to less than about 3 ppm (such about 0.5 to less than about 3ppm, about 1 to about 2.5, or about 1 to about 2 ppm hexanal) after 12 weeks of storage at about 70° F. to about 95° F. (in other approaches, about 70° F. to about 85° F.).
A packaging film may be provided including the volatile or semi-volatile antioxidants sourced from a toasted comestible byproduct as described herein. The packaging film may be a flexible packaging film. The antioxidants may include 4,6-substituted 2-methoxy phenols or derivatives thereof, or any antioxidant as described herein. In some embodiments, the packaging film or packaging material comprises a polymer substrate selected from polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate (EVA), polypropylene, polylactic acid (PLA), metalocene, polybutylene, and mixtures thereof.
In some embodiments, the flexible packaging film is a multi-layer film wherein one of the layers includes the amount of the antioxidants as described herein. Another of the layers in the multi-layer film may be a barrier layer selected from high density polyethylene (HDPE), polyvinylidene chloride (PVDC), ethylene-vinyl alcohol copolymer (EVOH), and combinations thereof. The packaging film may be a breathable or non-breathable film. The volatile or semi-volatile antioxidants described herein can be incorporated into a plastic liner, coated on the packaging, or laminated into a pouch. Alternatively, the natural antioxidants herein may be applied directly to a food.
The practice and advantages of the disclosed embodiments may be demonstrated by the following Examples, which are presented for purposes of illustration and not limitation. Unless indicated otherwise, all amounts, percentages, parts, and ratios of this disclosure and below Examples are by weight.
This Example describes screening experiments for natural and semi-volatile antioxidants. Three compounds were screened for their ability to prevent rancidity in a shelf-life study. The three compounds evaluated for antioxidant functionality included Sample A (2-methoxy-4-methylphenol, Sigma-Aldrich), Sample B (2,6-dimethoxy-4-vinylphenol, Sigma-Aldrich), and Sample C (2-methoxy-4-vinylphenol, Sigma-Aldrich).
Kellogg's unfrosted Mini-Wheats® cereal (shredded wheat cereal) was used in a shelf-life study comparing the preservative ability of the three compounds against a control with no added antioxidant (Sample D) and against a control with added BHT (Sample E, Sigma-Aldrich). For the evaluation, about 10 mg of each compound was placed inside a high barrier bag with the cereal at about 100° F. and about 35 percent relative humidity. The antioxidant sample was weighed and the appropriate amount added to the bag and then sealed.
Hexanal content is a marker to measuring rancidity of foods and about 3 ppm of released hexanal from a food is a threshold of perceived rancidity for most consumers. Hexanal content is measured by the following procedures: A cereal sample is removed at the appropriate shelf-life time point. About 0.5 grams of the cereal sample is mixed with about 5.0 mL of deionized water and sealed. About 0.5mL of headspace from the sealed sampled cereal is removed and the hexanal response is determined by GC with FID detection. The concentration of hexanal is determined based on a calibration curve made using hexanal standards in water. In part, the method is based upon: Hexanal as a Measure of Rancidity in Low Fat Foods, C. W. Fritsch, J. A. Gale, JAOCS, Volume 54, June 1977, p. 226-228 providing a list of the sources of information relating to the assay's development (ADAC, AACC, etc.), which is incorporated herein by reference.
As can be seen in Table 1, compounds A and C had a similar or better ability to mitigate the development of rancidity than the BHT control sample E. Compound B mitigated rancidity development in comparison to control sample D, but had a slightly weaker ability to mitigate rancidity compared to the BHT control Sample E.
Based on the screening study of Example 1, various food byproducts that could potentially provide the source of the selected compounds of Example 1 were identified. The food byproducts were then toasted, and the antioxidant activity of the toasted food byproducts was evaluated.
For this Example, canola meal (ADM), red wheat bran (Knappen Milling Company, Augusta, MI) and olive pomace (Il Fiorello Olive Oil Co., Fairfield, CA) were tested as sources of compounds capable of providing the compounds screened in Example 1. For example, it is believed that olive pomace upon toasting will produce 2-methoxy-4-methyl phenol; canola meal upon toasting will produce 2, 6-dimethoxy-4-vinyl phenol; and red wheat bran upon toasting will produce 2-methoxy-4-vinyl phenol. About 5 grams of each food byproduct was toasted at 230° C. for 20 minutes.
To evaluate the semi-volatile antioxidant functionality, the residue from the 5 gram toasted byproduct material (slightly less than 5 grams in mass) was placed inside a volatile—or semi-volatile-antioxidant test cell 100 as shown in
In this Example, a system was developed for capturing the antioxidants from the toasted food byproduct. A schematic of the system 200 is shown in
In an alternate example, cold trapping may include a flask connected to the outlet of the roaster, and immersed in an ice bath as shown in
This Example provide a longer shelf life study with antioxidants as described herein obtained from toasted food byproducts per the methods of Examples 1 to 3.
Volatilized and thermally converted compounds produced and captured according to the process in Examples 2 and 3 were extracted and tested in a shelf-life study. For this study, the samples of Table 3 below were evaluated for the prevention or control of hexanal generated from Unfrosted Mini-Wheats® cereal (shredded wheat cereal) over a period of 14 weeks. No BHT or any other antioxidant were added to the shredded wheat cereal during production, transportation, or storage until this experiment began.
For the evaluation, separate film pouches made from polyethylene film (film was permeable to the test samples) were filled with each of the test samples of Table 3 and then sealed. The procedure for samples K, L, and M: about 100 μL of an about 3000 ppm solution of each in methanol was placed in the pouch. The methanol was then evaporated under a gentle stream of dry nitrogen leaving about 300 μg of the dry pure compound in the pouch. The procedure for samples Q, U, and R: about 100 μL of an about 6000 ppm solution of each in methanol was placed in the pouch. The methanol was then evaporated under a gentle stream of dry nitrogen leaving about 600 μg of the extract in the pouch.
The pouch was then inserted into a package fabricated from high-barrier metalized film (high barrier metalized film prevents ingress or egress of oxygen, volatile, and semi-volatile organic molecules) along with about 20 grams of Unfrosted Mini-Wheats® cereal and the pouch and cereal were then sealed in the package. An empty film pouch was used as control sample J. The pouches were co-packed with the cereal and stored at about 100° F. for about 14 weeks. Every two weeks the hexanal content of the co-packed material was evaluated by hexanal-in-food analysis as described in Example 1. The hexanal content (ppm) over 14 weeks for each sample is shown in Table 4 below and
Example configurations are provided above so that this disclosure will be thorough, and will fully convey the scope of the disclosure to those of ordinary skill in the art. Specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of configurations of the present disclosure. It will be apparent to those of ordinary skill in the art that specific details need not be employed, that example configurations may be embodied in many different forms, and that the specific details and the example configurations should not be construed to limit the scope of the disclosure.
The terminology used herein is for the purpose of describing particular exemplary configurations only and is not intended to be limiting. As used herein, the singular articles “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are inclusive and therefore specify the presence of features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. Additional or alternative steps may be employed. If a range is described herein, it will be appreciated that any endpoint within the range may be included within this discussion.
The foregoing description has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular configuration are generally not limited to that particular configuration, but, where applicable, are interchangeable and can be used in a selected configuration, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.
This application claims the benefit of U.S. Provisional Application No. 62/687,576, filed Jun. 20, 2018, the entirety of which is hereby incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 62687576 | Jun 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17252011 | Dec 2020 | US |
| Child | 18661868 | US |
