WO1991011119A1 - Compositions and methods for inhibiting browning in foods - Google Patents
Compositions and methods for inhibiting browning in foods Download PDFInfo
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- WO1991011119A1 WO1991011119A1 PCT/US1991/000625 US9100625W WO9111119A1 WO 1991011119 A1 WO1991011119 A1 WO 1991011119A1 US 9100625 W US9100625 W US 9100625W WO 9111119 A1 WO9111119 A1 WO 9111119A1
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- resorcinol
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- 0 Cc(c(*)c1)ccc1O Chemical compound Cc(c(*)c1)ccc1O 0.000 description 1
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3553—Organic compounds containing phosphorus
-
- 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
- A23B4/10—Coating with a protective layer; Compositions or apparatus therefor
-
- 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
- A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
- A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
- A23B4/20—Organic compounds; Microorganisms; Enzymes
-
- 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
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
-
- 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
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3526—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
- C07C235/38—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/08—Dihydroxy benzenes; Alkylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
- C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
- C07C59/52—Unsaturated compounds containing hydroxy or O-metal groups a hydroxy or O-metal group being bound to a carbon atom of a six-membered aromatic ring
Definitions
- Browning of foods is a major problem in the food and beverage industry. Browning, or oxidative darkening, can be the result of the action of an enzyme, such as polyphenol oxidase (PPO), or the result of non-enzymatic chemical reactions, for example, due to polymerization of phenolic compounds which are present in some foods. High PPO activity is present in foods which are susceptible to PPO enzymes, such as polyphenol oxidase (PPO), or the result of non-enzymatic chemical reactions, for example, due to polymerization of phenolic compounds which are present in some foods. High PPO activity is present in foods which are susceptible to
- browning e.g., shrimp, bananas and mushrooms.
- Enzymatic browning in particular, has been the subject of much research, particularly as the causative agent of shrimp melanosis, which is characterized by the formation of dark spots on shrimp. Faulkner et al., Advanced Food Research, 19: 302-310 (1953). Enzymatic browning is the result of PPO-catalyzed oxidation of mono- and diphenols to o-quinones which polymerize spontaneously to form dark-colored, high molecular weight polymers, leading to the characteristic browning or formation of dark spots.
- sulfite salts Another method for reducing browning which has been prevalent in the food industry is adding sulfite salts to foods and beverages.
- Sulfites are also added to wines to prevent oxidation. Sulfites reduce o-quinones to the mono- and/or diphenols, thereby inhibiting the browning reaction.
- the use of sulfite in foods has been restricted due to adverse health effects in certain individuals, and may be
- the invention relates to compounds and methods for inhibiting oxidative browning of foods and beverages, particularly enzymatic browning caused by PPO activity.
- the compounds are resorcinol
- R 1 and R 2 are independently selected from the group consisting of: H, CH 3 , COR', CR',
- R 3 is an organic or inorganic substituent selected so that the resulting compound has
- R 3 can be a heteroatom or a group containing a heteroatom, a saturated or unsaturated alkyl group, a substituted aromatic compound or an organic functional group selected so that the compound has inhibitory
- the heteroatom can include, for example, oxygen (O), nitrogen (N), sulfur (S), phosphorus (P) or halogens such as chlorine (Cl), bromine (Br), iodine (I) or fluorine (F).
- the saturated or unsaturated alkyl group can have from 1 to 30 carbon atoms in a linear, branched or cyclic configuration and can include a substituted aromatic compound.
- the alkyl substitutents or organic functional groups can contain a heteroatom or heteroatoms, for example oxygen (O), nitrogen (N), sulfur (S), phosphorus (P) or halogens such as chlorine (Cl), bromine (Br), iodine (I) or fluorine (F).
- 4-Alkyl resorcinol compounds are particularly effective for inhibiting me l ano s i s in mos t foods . For examp le ,
- R 3 has the general formula
- n 1 or 2 and Z is an alkyl or other organic functional group selected so that the compound has inhibitory activity.
- Z can be an alkyl substituent containing at least one heteroatom, such nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) or halogens such as chlorine (Cl), bromine (Br), iodine (I) or fluorine (F).
- N nitrogen
- O oxygen
- S sulfur
- P phosphorus
- halogens such as chlorine (Cl), bromine (Br), iodine (I) or fluorine (F).
- Z is selected from the group consisting of: OH, NH 2 , O(CH 2 ) x CH 3 , NHCO 2 (CH 2 ) x CH 3 ,
- NH(CH 2 ) x CH 3 amino acids, polyamine metaboletes, such as NH(CH 2 ) x NH 2 ; NH(CH 2 ) x NH(CH 2 ) y NH 2 ;
- x and y independently can be any integer from 0 to 5; and higher polyamine oligomers or substituted oligomers consisting of at least three monomers, wherein the monomer is a 1, ⁇ diaminoalkane and R 4 has the following formula:
- n, R 1 and R 2 are as defined above.
- inhibitors of oxidative browning are resorcinol derivatives having the general formula:
- n 1 or 2 and R 1 and R 2 and Z are as defined above.
- R 4 is as defined above). These compounds are shown as Formulae IV, V, VI and VII respectively:
- Formula V, VI and VII represent polyamine
- Formula IV represents a resorcinol derivative which had not previously been found in nature.
- resorcinol derivatives can be prepared synthetically or isolated from natural sources, such as plants.
- the derivatives are isolated and purified. to homogeneity from a botanical source, e.g., fig latex, by the steps of aqueous extraction, ultrafiltration, ion exchange chromatography and reverse phase HPLC.
- a method of inhibiting browning of foods using the present compounds is described.
- foods which are susceptible to browning including, for example, certain shellfish, crustaceans, fruits, vegetables and beverages, such as fruit juices and wines are treated with a composition containing an amount of the present resorcinol derivatives sufficient to inhibit the browning reaction.
- the present resorcinol derivatives represented generally by Formulae I and III, and specifically by Formulae II and IV, and the resorcinol-polyamine derivatives represented specifically by Formulae V, VI and VII, are very effective in inhibiting
- compositions and methods are more effective than crude latex
- the present compounds provide an effective treatment for inhibiting or preventing browning in selected foods and beverages, without adversely affecting the appearance, taste, texture or quality of the food or beverage.
- Figure 1 is a graph comparing the effects of sodium bisulfite and various concentrations of a YM5 extract (F100) on the formation of melanosis in shrimp.
- Figure 2 is a graph comparing the effects of sodium bisulfite, various concentrations of ficin and a YM5 extract (F100) on the formation of
- Figure 3 is a graph comparing the effects of sodium bisulfite, a YM5 extract (1% by wt.) and the compound of Formula V (0.1% by wt.) on the formation of melanosis in shrimp.
- Figure 4 is a graph comparing the effects of sodium bisulfite and various concentrations of the compound of Formula V on the formation of melanosis in shrimp.
- Figure 5 is a schematic illustration of showing the synthesis steps for the compounds of Formula V and Formula VII.
- Figure 6 is a graph comparing the effects of various concentrations of the compound of Formula V on the formation of melanosis in fresh pink shrimp; that is, shrimp which were not frozen prior to treatment.
- Figure 7 is a graph comparing the effect of no rinse and a post-treatment sea water rinse on the inhibition of shrimp melanosis by 0.025% of the compound of Formula V.
- Figure 8 is a graph comparing the inhibition of shrimp melanosis by a sea water or fresh water solution of 0.01% the compound of Formula V.
- Figure 9 is a graph comparing the inhibition of shrimp melanosis upon repeated dips of different one pound batches of untreated shrimp into the same one liter of 0.01% the compound of Formula V solution in sea water.
- Figure 10 is a graph comparing the effect of sodium bisulfite, sea water, and various
- Figure 11 is a graph comparing the effect of sodium bisulfite, sea water, and various
- Figure 12 is a graph comparing the effect of sodium bisulfite, sea water, and various
- Figure 13 is a graph comparing the effect of sodium bisulfite, sea water, and various
- the present invention is based on the discovery that a class of resorcinol derivatives, some of which occur naturally in plants, can inhibit
- the present compounds are resorcinol derivatives which have the general formula shown as Formula I:
- R 1 and R 2 are independently selected from the group consisting of: H, CH 3 , COR', CR',
- R 3 independently H or an alkyl group having from about 1 to about 6 carbon atoms in a linear, branched or cyclic configuration or a substituted aromatic compound; R 3 can be a heteroatom or a group
- the unsaturated alkyl group can have, for example, oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), halogen such as chlorine (Cl), bromine (Br), or fluorine (F).
- the saturated or unsaturated alkyl group can have from 1 to 30 carbon atoms in a linear branched, or cyclic configuration or a substituted aromatic compound.
- the alkyl substitutents or organic functional group can contain a heteroatom or
- heteroatoms for example oxygen (O), nitrogen (N), sulfur (S), phosphorus (P) or a halogen such as chlorine (Cl), bromine (Br), iodine (I) or fluorine (F).
- Alkyl resorcinol compounds are particularly effective for inhibiting melanosis in most foods.
- 4-hexylresorcinol which has the following formula:
- R 3 has the general structure
- Z is an alkyl or organic functional group selected so that the compound has inhibitory activity.
- Z can be an alkyl substituent containing at least one heteroatom, for example, nitrogen (N), oxygen (0), sulfur (S) and phosphorus (P) or a halogen such as chlorine (Cl), bromine (Br), iodine (I) or fluorine (F).
- Z is selected from the group consisting of: OH, NH 2 , O(CH 2 ) x CH 3 , NHCO 2 (CH 2 )xCH 3 ,
- amino acids such as lysine, ornithine, serine or cysteine
- a polyamine metabolite such as
- x and y can be an integer from 0 to 5; and polyamine oligomers or substituted polyamine oligomers consisting of at least three monomers, wherein the monomer is a 1, ⁇ diaminoalkane and R 4 has the following formula:
- n, R 1 and R 2 are as defined above.
- inhibitors of oxidative browning are resorcinol derivatives having the following general formula:
- n 1 or 2 and R 1 , R 2 and Z are as defined above.
- a molecule is said to be a "derivative" of another molecule when it contains additional or different chemical moieties not normally part of the molecule.
- diaminobutane and the polyamine spermidine, are amino-acid derived aliphatic nitrogeneous compounds widely distributed throughout the plant and animal kingdoms. Flores, H.E., Protacio, C.M., and Signs, M.W. (1989) In PIant Nitrogen Metabolism, In:
- HCA hydroxycinnamic amide
- HCAs are closely related in structure to Formulae V, VI and VII. Although much research is currently being performed on HCAs, there are no prior accounts in the literature on the presence of Formulae V, VI and VII. Formulae V and VII are novel,
- the compound of Formula VI which has not been found in nature at this time, also represents a previously unknown polyamine derivative. Besides their
- the compounds represented by Formulae V, VI and VII represent a novel class of polyamine derivatives whose distribution, metabolism and physiological effects are unknown.
- the molecules shown as Formulae IV, V and VII can be purified from plants. Preparations from various botanical sources are effective inhibitors of certain enzymatic reactions. For example, latex derived from the fig tree, Ficus sp. (F. sp.)
- ficin treatment is detrimental to the texture and quality of foods because ficin's proteolytic activity degrades protein in the foods.
- a commercial latex extract prepared from fig latex can be used as the starting material.
- Fig latex extracts contain ficin and other compounds and are referred to as "crude ficin” or "crude ficin extracts”.
- Crude ficin extracts are useful as a source for obtaining Formulae IV, V and VII because these extracts are commercially available.
- Crude ficin extracts are generally available in solid form, as a powder or tablet. The crude ficin preparations are
- the major protease component is ficin, a protein having a molecular weight of about 20,000 daltons.
- ficin a protein having a molecular weight of about 20,000 daltons.
- the presence of ficin can be detected by a method which separates materials based on molecular weight, such as, for example, gel permeation-high performance liquid chromatography (GPC-HPLC), and by the ficin-catalyzed hydrolysis of benzoyl-L-arginine-p-nitroanilide (L-BAPNA), which is a sensitive assay for ficin activity.
- GPC-HPLC gel permeation-high performance liquid chromatography
- L-BAPNA benzoyl-L-arginine-p-nitroanilide
- Formula I represents several commercially available compounds, such as alkylresorcinols, which have been used for other applications. Applicants have now discovered that compounds having the structure shown as Formula I are effective
- anti-browning compounds represented by Formulae II and IV-VII can be prepared by synthetic methods.
- Formula V is synthesized according to the following general procedure which is set out in detail in Example 5:
- the synthesized compound is identical to the compound isolated from the crude ficin extract, as determined by 1 H and 13 C NMR, mass spectral analysis, elemental analysis and TLC .
- Formulae V and VII can be synthesized according to the following procedure, which is shown
- (1,3-dihydroxybenzene) is derivatized by treatment with a reagent which results in the addition of one C atom to an aromatic ring, e.g., Gatterman reagent (Zn(CN) 2 , HCl) or Vlllsmeier reagent (POCl 3 /DMF), to add an aldehyde group to the ring thereby forming
- a reagent which results in the addition of one C atom to an aromatic ring
- Gatterman reagent Zn(CN) 2 , HCl
- Vlllsmeier reagent POCl 3 /DMF
- 2,4-dihydroxybenzaldehyde This compound is further reacted with malonic acid (CH 2 (COOH) 2 ) in a basic organic solvent such as pyridine and piperidine, at an elevated temperature (e.g., about 100° to 140°C) to yield 2,4-dihydroxycinnamic acid.
- a basic organic solvent such as pyridine and piperidine
- an elevated temperature e.g., about 100° to 140°C
- the double bond in the side chain of 2,4-dihydroxycinnamic acid is hydrogenated, for example using hydrogen and palladium, to form 2,4-dihydroxyphenylpropionic acid. Reaction of this compound with an excess of diaminobutane yields Formula V
- the present resorcinol derivatives can be applied to various foods and beverages to prevent or inhibit browning, particularly enzymatic browning.
- browning refers to oxidative darkening or discoloration resulting from the formation of o-quinone and quinone polymers which result from the action of PPO in forming quinones or from the polymerization of quinones, and with other components, which occur naturally in foods.
- the resorcinol derivatives are used to treat the food or beverage in an amount or concentration sufficient to inhibit or prevent browning.
- the form of treatment will depend upon the food or beverage being treated, and the results sought, and can include, e.g., dipping, spraying, dusting, sprinkling, immersing, mixing and/or soaking.
- the compounds can be added to an aqueous diluent, for example water, salt water or buffer, and applied to the food, or can be added neat, e.g., to fruit juice.
- the amount needed will depend upon the susceptibility of the food or beverage to browning, the condition of the food and the storage conditions. The amount sufficient to prevent or inhibit browning can be determined empirically by one skilled In the food art.
- pink shrimp were treated with an aqueous solution of the compound of Formula II.
- Formula II was used at concentrations ranging from 0.0001 to 0.005%, and compared to shrimp treated with sodium bisulfite and sea water. The results are shown In Figure 10.
- the sea water treated shrimp developed melanosis spots within 1-2 days.
- Formula II was more effective on a weight basis than sodium bisulfite in Inhibiting browning of the shrimp. For example, a solution containing as little as 0.005% by weight of Formula II was almost as effective in inhibiting shrimp melanosis as a solution of 1.25% by weight
- a concentration of up to about 0.1% of Formula II can be used for inhibiting browning.
- pink shrimp were treated with an aqueous solution of Formula V prepared as described herein.
- Formula V was used at concentrations ranging from about 0.1% by weight to about 0.001% by weight and compared to shrimp treated with sodium bisulfite, and untreated shrimp. The results are shown in Figure 4. The untreated shrimp quickly developed black spots
- Formula V was more effective on a weight basis than sodium bisulfite in inhibiting browning of the shrimp.
- a solution containing as little as about 0.005% by weight of Formula V was as effective in inhibiting shrimp melanosis as a solution of 1.25% by weight of sodium bisulfite.
- a concentration of about 0.1% by weight of the present resorcinol derivatives is
- compositions and methods of the present invention are useful in preventing or significantly inhibiting browning in many foods and beverages which are susceptible to browning.
- foods and beverages include, but are not limited to, shrimp, potatoes, apples, bananas, lettuce, peaches, wines and some fruit juices.
- the present composition does not cause degradation of foods, particularly shrimp. Browning is "prevented” if it is completely
- Browning is "significantly inhibited” if browning takes place at a significantly lower rate compared to untreated foods in the same time frame.
- YM5 eluate The ultrafIltered eluate was referred to as the "YM5 eluate".
- the 0.45 ⁇ -filtrate and the YM5 -ultrafiltered material were analyzed by gel permeation chromatography-high performance liquid chromatography (GPC-HPLC) and found to be free of any "absorbance at 214 nm in the retention time range corresponding to ficin. Also, no ficin activity was detected in the YM5 eluate using the chromophoric substrate benzoyl-L-arginine- p-nitro-anilide (L-BAPNA).
- the model assay system consisted of the
- L-DOPA L-dihydroxyphenylalanine
- YM5 preparations in a 1 mL total volume.
- Reverse phase HPLC is a purification method based on the separation of molecules according to their interaction with a hydrophobic stationary phase within an HPLC column as the hydrophobicity of the mobile phase increases.
- the stationary phase column packing
- the mobile phase the solvent which flows through the column
- TFA trifluoroacetic acid
- a purification protocol was developed on an analytical scale and then adapted to the preparative scale using a Waters DeltaPrep HPLC system. (Waters Associates,
- Example 1 The YM5 eluate obtained In Example 1 was
- the eluted material was monitored for absorbance at 214 and 280 nm, and collected in 20 mL fractions. The total gradient volume was two liters. Fractions were tested for the presence of inhibitor using the model assay system described in Example 1. Five peaks of inhibition were found upon analysis. The fractions found under these peaks were pooled, frozen, and lyophilized. Two peaks labeled Pool IV and Pool V appeared to be the most potent inhibitors based on the ratio of % inhibition to peak size, and were chosen for further purification with RP-HPLC, as described in Example 2.
- the lyophilized material from SP-Sephadex Pool IV was dissolved in the mobile phase, centrifuged to remove particulates, and loaded onto the HPLC column. A linear gradient of increasing
- acetonitrile concentration was developed and the inhibitor eluted at about 15% acetonitrile.
- the eluant was monitored at 214 and 280 nm with a multichannel UV-Vis detector and in certain runs the fractions were assayed to confirm the presence of the inhibitor.
- the peak inhibitor fractions were pooled, concentrated in a SpeedVac, frozen, and lyophilized. Re-analysis by RP-HPLC in a
- TFA/methanol gradient system indicated a high degree of purity for the recovered inhibitor.
- the purified Pool IV inhibitor was analyzed by several physical methods and chemical tests. A UV-Vis spectrum of the inhibitor showed an
- the conditions for the purification were the same as those used in Example 2.
- a linear gradient of increasing acetonitrile concentration was developed and the compound, Formula VII, eluted at about 30% acetonitrile.
- the eluant was monitored at 214 and 280 nm with a multichannel UV-Vis detector and in certain runs the fractions were assayed to confirm the presence of the inhibitor, represented by
- reaction mixture was then filtered over a bed of Celite (Rohm and Haas Co.,
- the compound represented by Formula VI (bis-2,4-dihydroxyphenylpropionyldiaminobutane) was synthesized by a modification of the procedure described in Example 5. Diaminobutane (1.09 mL, 5.48 mmoles) was dissolved in 30 mL absolute
- Example 2 (mushroom), a linear spectrophotmetric assay system similar to that described in Example 1 was used.
- the assay mixture consisted of:
- L-DOPA L-dihydroxyphenylalanine
- the rate of the reaction was monitored by measuring the change in absorbance per minute at 475 nm at 25°C.
- the apparent inhibition constants (I 50 ) are shown in Table 1. I 50 represents the concentration of inhibitor necessary to obtain fifty (50%) percent inhibition of the enzyme. The results show that much lower concentrations of the resorcinol derivatives were needed to reach the same level of inhibition compared to resorcinol.
- the melanosis scale can be related to existing recommendations developed by the National Marine Fisheries Service for grading raw shrimp. Code of Federal Regulations (1982) Title 50, Part 265, Subpart A, United States General standards for Grades of Shrimp, pp. 262-268.
- a scale rating of 4 or greater represents a measurable defect in product quality.
- a rating of 8 or greater would represent a severe defect approaching an unacceptable product.
- Example 1 included tap water as a control, sodium bisulfite at a concentration of 1.25%, crude EDC ficin and the YM5 eluate prepared according to the procedure outlined in Example 1, which is designated "F100'' .
- the dip solution was fresh tap water.
- the treatments contained variable additions to tap water, unless otherwise specified in batches made with distilled water. All treatments were complete submergence of the shrimp in the dips for 60 to 80 seconds followed by brief (5-10 seconds) colander drain with mild agitation.
- Figure 1 shows that the YM5 eluate, F100, was as effective as, or better than, sodium bisulfite in reducing melanosis.
- Figure 2 shows that F100 was as effective as crude ficin and more effective than sodium bisulfite in reducing melanosis.
- Example 9 Inhibition of Enzymatic Browning of Apples by YM5 Eluate
- the apple slices were allowed to stand at ambient temperature, exposed to air. The slices were checked visually for browning after 0, 1, 2, 3, 4 and 24 hours.
- the basic procedure was to rinse the shrimp in variable dip compositions and concentrations for 1 minute (for test solutions containing the two highest concentrations of the Formula V compound, i.e., 0.1% and 0.05%, due to lack of sufficient material, the test solution was painted onto 6 individual shrimp), then drain and package in plastic bags to be stored in ice. The bags were considered necessary to eliminate the variable influence of melting ice. Iced containers with packaged shrimp were stored in 35°F (1.7oC)
- Formula II (4-hexylresorcinol, Sigma Chemical Co.) was substituted for the Formula V compound. Pink shrimp were dipped into solutions of 0.0001 - 0.005% of the Formula II compound and stored as described above. The data is graphed in Figure 10 and shows the Formula II compound to be a potent inhibitor of the formation of shrimp melanosis at concentrations as low as 0.0005%.
- Example 17 The Effect of the Formula VI Compound on the
- Pink shrimp were treated and evaluated as described in Example 8 except that the compound of Formula IV (2,4-dihydroxy ⁇ henylpropionic acid) was substituted for the Formula V compound. Pink shrimp were dipped into solutions of 0.001 - 0.1% the
- PPO was isolated from Taiwanese Black Tiger Shrimp (Penaeus monodon) according to the following procedure: Tiger shrimp heads were frozen in liquid nitrogen and then ground to a fine powder. The powdered shrimp heads were extracted into phosphate buffer by stirring. The crude extracts were
- a control run was made as follows: A 50 ⁇ l aliquot of 5 mM sodium phosphate (pH 6.5) was added to 880 ⁇ l of 5 mM L-DOPA, 5 mM sodium phosphate (pH 6.5). 70 ⁇ l of Tiger shrimp PPO (6.3 mg total protein stock solution) were added and the reaction was Immediately monitored using a Beckman DU
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91904487A EP0514467B1 (en) | 1990-02-05 | 1991-01-30 | Compositions and methods for inhibiting browning in foods |
DE69103406T DE69103406T2 (en) | 1990-02-05 | 1991-01-30 | METHOD AND COMPOSITIONS FOR INHIBITING BROWNING OF FOODSTUFFS. |
JP03504881A JP3093788B2 (en) | 1990-02-05 | 1991-01-30 | How to inhibit food browning |
CA002074352A CA2074352C (en) | 1990-02-05 | 1991-01-30 | Compositions and methods for inhibiting browning in foods |
Applications Claiming Priority (4)
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US47515090A | 1990-02-05 | 1990-02-05 | |
US07/537,361 US5059438A (en) | 1990-02-05 | 1990-06-13 | Compositions and methods for inhibiting browning in foods using resorcinol derivatives |
US475,150 | 1990-06-13 | ||
US537,361 | 1990-06-13 |
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WO1991011119A1 true WO1991011119A1 (en) | 1991-08-08 |
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PCT/US1991/000625 WO1991011119A1 (en) | 1990-02-05 | 1991-01-30 | Compositions and methods for inhibiting browning in foods |
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US (2) | US5059438A (en) |
EP (1) | EP0514467B1 (en) |
JP (3) | JP3093788B2 (en) |
AT (1) | ATE109626T1 (en) |
AU (1) | AU7321291A (en) |
CA (1) | CA2074352C (en) |
DE (1) | DE69103406T2 (en) |
DK (1) | DK0514467T3 (en) |
ES (1) | ES2063497T3 (en) |
WO (1) | WO1991011119A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992022213A1 (en) | 1991-06-10 | 1992-12-23 | Opta Food Ingredients, Inc. | Compositions and methods for inhibiting browning in foods and beverages |
EP0904774A1 (en) * | 1997-09-23 | 1999-03-31 | Pfizer Products Inc. | Resorcinol derivatives |
US6828460B2 (en) | 1999-03-22 | 2004-12-07 | Pfizer Inc. | Resorcinol derivatives |
US6878381B2 (en) | 1999-03-22 | 2005-04-12 | Pfizer, Inc | Resorcinol composition |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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US5059438A (en) * | 1990-02-05 | 1991-10-22 | Enzytech, Inc. | Compositions and methods for inhibiting browning in foods using resorcinol derivatives |
JPH05167472A (en) * | 1991-12-12 | 1993-07-02 | Matsushita Electric Ind Co Ltd | Responder for mobile object identification |
US6160204A (en) * | 1992-01-31 | 2000-12-12 | Cornell Research Foundation, Inc. | Polyphenol oxidase cDNA |
US6054160A (en) * | 1997-07-14 | 2000-04-25 | Epl Technologies, Inc. | Compositions and processes for maintaining the fresh sensory attributes of freshly-cut apples |
US6428461B1 (en) | 2001-04-24 | 2002-08-06 | Kraft Foods Holdings, Inc. | Method for inhibiting oxidation of polyunsaturated lipids |
US20040028786A1 (en) * | 2001-07-03 | 2004-02-12 | Tomoko Tani | Methods of freezing and thawing food, method of freezing, thawing, and cooking foods, devices for freezing and thawing food, device of freezing, thawing, and cooking food, and frozen food |
US20030203082A1 (en) * | 2002-04-30 | 2003-10-30 | Givaudan Sa | Inhibition of non-enzymatic browning |
JP4552459B2 (en) * | 2003-02-28 | 2010-09-29 | チッソ株式会社 | Polyamine-polyphenol hybrid and radical scavenger |
JP5490907B2 (en) * | 2009-10-09 | 2014-05-14 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Latent curing agent and epoxy composition containing the latent curing agent |
CN102669263B (en) * | 2012-06-01 | 2013-08-21 | 新疆农业大学 | Method for improving normal-temperature fresh-preservation effect of saimaiti apricots |
CN116806830A (en) * | 2022-09-14 | 2023-09-29 | 江苏省农业科学院 | Application of lysobacter source ferrite |
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US4981708A (en) * | 1989-10-02 | 1991-01-01 | Enzytech, Inc. | Method of preventing browning in foods utilizing protease free latex extracts particularly from figs |
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US3337348A (en) * | 1966-04-20 | 1967-08-22 | Gen Foods Corp | Process for preventing chemical browning in moist and dry food material |
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ES414753A1 (en) * | 1973-05-14 | 1976-05-01 | Gutix Sa | Procedure for the production of useful compositions in the conservation of crustaceans avoiding the call melanosis. (Machine-translation by Google Translate, not legally binding) |
DE2721398A1 (en) * | 1976-05-19 | 1977-12-01 | Ciba Geigy Ag | ALKYLPHENOL STABILIZERS |
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-
1991
- 1991-01-30 JP JP03504881A patent/JP3093788B2/en not_active Expired - Fee Related
- 1991-01-30 ES ES91904487T patent/ES2063497T3/en not_active Expired - Lifetime
- 1991-01-30 AT AT91904487T patent/ATE109626T1/en not_active IP Right Cessation
- 1991-01-30 DK DK91904487.5T patent/DK0514467T3/en active
- 1991-01-30 CA CA002074352A patent/CA2074352C/en not_active Expired - Lifetime
- 1991-01-30 DE DE69103406T patent/DE69103406T2/en not_active Expired - Fee Related
- 1991-01-30 AU AU73212/91A patent/AU7321291A/en not_active Abandoned
- 1991-01-30 EP EP91904487A patent/EP0514467B1/en not_active Expired - Lifetime
- 1991-01-30 WO PCT/US1991/000625 patent/WO1991011119A1/en active IP Right Grant
- 1991-10-21 US US07/780,721 patent/US5304679A/en not_active Expired - Lifetime
-
2000
- 2000-02-28 JP JP2000050670A patent/JP2000247937A/en active Pending
- 2000-10-26 JP JP2000327299A patent/JP3582717B2/en not_active Expired - Fee Related
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WO1988002602A1 (en) * | 1986-10-08 | 1988-04-21 | Dumbroff Erwin B | Control of senescence in fruits, vegetables and flowers |
US4981708A (en) * | 1989-10-02 | 1991-01-01 | Enzytech, Inc. | Method of preventing browning in foods utilizing protease free latex extracts particularly from figs |
Cited By (13)
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WO1992022213A1 (en) | 1991-06-10 | 1992-12-23 | Opta Food Ingredients, Inc. | Compositions and methods for inhibiting browning in foods and beverages |
EP0587776A1 (en) * | 1991-06-10 | 1994-03-23 | Opta Food Ingredients, Inc. | Use of compositions and methods for inhibiting browning in foods and beverages |
EP0587776A4 (en) * | 1991-06-10 | 1994-04-13 | Opta Food Ingredients, Inc. | |
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AP857A (en) * | 1997-09-23 | 2000-07-11 | Pfizer Prod Inc | Resorcinol derivatives. |
EP0904774A1 (en) * | 1997-09-23 | 1999-03-31 | Pfizer Products Inc. | Resorcinol derivatives |
AU735716B2 (en) * | 1997-09-23 | 2001-07-12 | Pfizer Products Inc. | Resorcinol derivatives |
CZ297669B6 (en) * | 1997-09-23 | 2007-02-28 | Pfizer Products Inc. | Topical pharmaceutical composition for lightening skin, tyrosinase inhibiting topical composition and topical or transdermal composition for treating inflammatory diseases containing resorcinol derivative and corresponding medicaments |
AU735716C (en) * | 1997-09-23 | 2007-03-29 | Pfizer Products Inc. | Resorcinol derivatives |
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US6933319B2 (en) | 1999-03-22 | 2005-08-23 | Pfizer Inc. | Resorcinol derivatives |
Also Published As
Publication number | Publication date |
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US5059438A (en) | 1991-10-22 |
EP0514467A1 (en) | 1992-11-25 |
US5304679A (en) | 1994-04-19 |
CA2074352A1 (en) | 1991-08-06 |
ATE109626T1 (en) | 1994-08-15 |
JP2001169763A (en) | 2001-06-26 |
DK0514467T3 (en) | 1995-01-02 |
CA2074352C (en) | 2002-09-17 |
DE69103406T2 (en) | 1995-04-20 |
DE69103406D1 (en) | 1994-09-15 |
JPH05508533A (en) | 1993-12-02 |
ES2063497T3 (en) | 1995-01-01 |
AU7321291A (en) | 1991-08-21 |
JP3582717B2 (en) | 2004-10-27 |
JP2000247937A (en) | 2000-09-12 |
EP0514467B1 (en) | 1994-08-10 |
JP3093788B2 (en) | 2000-10-03 |
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