US4369197A
Expired / Lapsed
US
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Bulk preservative storage of horticultural crops and pigments produced from green horticultural crops
Assignee: Ohio Agricultural Research and Development Center
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Filing: 1981-01-28
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Granted: 1983-01-18
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Expires: 2001-01-28
Abstract
Abstract Horticultural crops may be stored in an acidic aqueous liquor at a temperature not exceeding about room temperature wherein the pH of the liquor is sufficiently low and the storage conditions are adequately starved of molecular oxygen to retard spoilage of the stored product. Following termination of the storage, the stored product is preferably at least partially neutralized at a temperature of between about 40° and 60° F. with a neutralizing agent to raise the pH of the stored product. When green horticultural crops are thus stored and thereafter boiled, a strong green coloration is produced and green pigments can be separated by solvent extraction.
Inventors
- 👤 Richard M. Basel
- 👤 Wilbur A. Gould
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 08:22
CPC Classifications
C; C09; C09B; C09B61/00; A; A23; A23B; A23B7/00; A23B7/10; Y; Y02; Y02A; Y02A40/00; Y02A40/90
Claims Analysis
Total Claims: 44
Claim 1
Independent Claim
118 words
A composition of matter comprising a green pigment derived from chlorophyll and substantially free from copper, said pigment being more soluble in petroleum ether than in acetone, having a R f value of about 0.0286 when developed with a 74% methanol: 20% acetone: 6% water mixture saturated with soybean oil using microcrystalline cellulose reversed phase thin layer chromatography and having the following spectroscopic characteristics: (a) visible peaks in either solution at about 410 and about 665 nm; (b) infra-red peaks at about 2920, about 2850, about 1710, about 1460 and about 1375 cm -1 , and (c) nuclear magnetic resonance peaks in 100% deuterochloroform at about -3.521, about 7.260 and about 5.363 parts per million relative to tetramethylsilane.
Claim 2
Dependent Claim
118 words
A composition of matter comprising a green pigment derived from chlorophyll and substantially free from copper, said pigment being more soluble in petroleum ether than in acetone, having a R f value of about 0.0286 when developed with a 74% methanol: 20% acetone: 6% water mixture saturated with soybean oil using microcrystalline cellulose reversed phase thin layer chromatography and having the following spectroscopic characteristics: (a) visible peaks in either solution at about 410 and about 665 nm; (b) infra-red peaks at about 2920, about 2850, about 1710, about 1460 and about 1375 cm -1 , and (c) nuclear magnetic resonance peaks in 100% deuterochloroform at about -3.521, about 7.260 and about 5.363 parts per million relative to tetramethylsilane.
Claim 3
Dependent Claim
142 words
A composition of matter comprising a green, paramagnetic, copper-containing pigment derived from chlorophyll, said pigment being more soluble in petroleum ether than in acetone, stable in boiling 20% hydrochloric acid and stable to 50% aqueos sodium hydroxide solution, having an R f value of about 0.0091 when developed with a 74% methanol: 20% acetone: 6% water mixture saturated with soybean oil using microcrystalline cellulose reversed phase thin layer chromatography, and having the following spectroscopic characteristics: (a) visible peaks in ether solution at about 420 and about 644 nm; (b) infra-red peaks at about 2920, about 2850, about 1710, about 1460 and about 1410 cm -1 ; (c) nuclear magnetic resonance peaks in 100% deuterochloroform at about -3.521, about 7.260 and about 5.359 parts per million relative to tetramethylsilane; and (d) electron spin resonance at about 3222 G at 77° K. in pyridine.
Claim 4
Dependent Claim
142 words
A composition of matter comprising a green, paramagnetic, copper-containing pigment derived from chlorophyll, said pigment being more soluble in petroleum ether than in acetone, stable in boiling 20% hydrochloric acid and stable to 50% aqueos sodium hydroxide solution, having an R f value of about 0.0091 when developed with a 74% methanol: 20% acetone: 6% water mixture saturated with soybean oil using microcrystalline cellulose reversed phase thin layer chromatography, and having the following spectroscopic characteristics: (a) visible peaks in ether solution at about 420 and about 644 nm; (b) infra-red peaks at about 2920, about 2850, about 1710, about 1460 and about 1410 cm -1 ; (c) nuclear magnetic resonance peaks in 100% deuterochloroform at about -3.521, about 7.260 and about 5.359 parts per million relative to tetramethylsilane; and (d) electron spin resonance at about 3222 G at 77° K. in pyridine.
Claim 5
Independent Claim
103 words
A method of preparing a green pigment substantially free from copper, which process comprises: storing an edible horticultural product containing chlorophyll but substantially free from copper in an acidic aqueous liquor at a temperature above freezing but not exceeding about room temperature, the pH of said liquor being sufficiently low and said storage conditions being adequately starved of molecular oxygen to retard spoilage of said stored product; at least partially neutralizing said stored product; heating said stored and neutralized product to produce said pigment therein; extracting said pigment from said product with a non-polar solvent; and evaporating said non-polar solvent from said extract.
Claim 6
Independent Claim
103 words
A method of preparing a green pigment substantially free from copper, which process comprises: storing an edible horticultural product containing chlorophyll but substantially free from copper in an acidic aqueous liquor at a temperature above freezing but not exceeding about room temperature, the pH of said liquor being sufficiently low and said storage conditions being adequately starved of molecular oxygen to retard spoilage of said stored product; at least partially neutralizing said stored product; heating said stored and neutralized product to produce said pigment therein; extracting said pigment from said product with a non-polar solvent; and evaporating said non-polar solvent from said extract.
Claim 7
Independent Claim
110 words
A method of preparing a green, copper-containing pigment, which method comprises: storing an edible horticultural product containing chlorophyll in an acidic aqueous liquor at a temperature above freezing but not exceeding about room temperature, the pH of said liquor being sufficiently low and said storage conditions being adequately starved of molecular oxygen to retard spoilage of said stored product; at least partially neutralizing said stored product; adding copper to said stored and neutralized product if copper is not already contained therein; heating said stored and neutralized product to produce said pigment therein; extracting said pigment from said product with a non-polar solvent; and evaporating said non-polar solvent from said extract.
Claim 8
Independent Claim
110 words
A method of preparing a green, copper-containing pigment, which method comprises: storing an edible horticultural product containing chlorophyll in an acidic aqueous liquor at a temperature above freezing but not exceeding about room temperature, the pH of said liquor being sufficiently low and said storage conditions being adequately starved of molecular oxygen to retard spoilage of said stored product; at least partially neutralizing said stored product; adding copper to said stored and neutralized product if copper is not already contained therein; heating said stored and neutralized product to produce said pigment therein; extracting said pigment from said product with a non-polar solvent; and evaporating said non-polar solvent from said extract.
Claim 9
Dependent Claim
43 words
A method according to claim 3 or 4 wherein said pigment is extracted from said product with a semi-polar solvent, said semi-polar solvent extract is thereafter extracted with a non-polar solvent, and said non-polar solvent extract is separated from said semi-polar solvent extract.
Claim 10
Dependent Claim
12 words
A method according to claim 5 wherein said semi-polar solvent is acetone.
Claim 11
Dependent Claim
15 words
A method according to claim 3 or 4 wherein said non-polar solvent is petroleum ether.
Claim 12
Dependent Claim
16 words
A method according to claim 3 or 4 wherein said acidic aqueous liquor contains hydrochloric acid.
Claim 13
Dependent Claim
25 words
A method according to claim 3 or 4 wherein the level of molecular oxygen under said storage conditions does not substantially exceed about 25 ppm.
Claim 14
Dependent Claim
16 words
A method according to claim 3 or 4 wherein said edible horticultural product comprises green beans.
Claim 15
Independent Claim
137 words
A method for the preservative storage of a solid edible horticultural product not previously subjected to a sterilization process selected from the group consisting of sterilization and pasteurization, which comprises: storing said product for at least about one week in an acidic liquor having a pH not greater than about 2 and an oxygen concentration not exceeding about 100 parts per million at a temperature above freezing, but not exceeding about room temperature, the acidity and oxygen concentration of said liquor serving to retard spoilage of said stored product; and at least partially neutralizing said stored product at a temperature of above freezing but not exceeding about room temperature with a neutralizing agent at the termination of said storage to raise the pH of said stored product to an acceptable level for use of said stored product.
Claim 16
Independent Claim
137 words
A method for the preservative storage of a solid edible horticultural product not previously subjected to a sterilization process selected from the group consisting of sterilization and pasteurization, which comprises: storing said product for at least about one week in an acidic liquor having a pH not greater than about 2 and an oxygen concentration not exceeding about 100 parts per million at a temperature above freezing, but not exceeding about room temperature, the acidity and oxygen concentration of said liquor serving to retard spoilage of said stored product; and at least partially neutralizing said stored product at a temperature of above freezing but not exceeding about room temperature with a neutralizing agent at the termination of said storage to raise the pH of said stored product to an acceptable level for use of said stored product.
Claim 17
Dependent Claim
22 words
The method of claim 11 wherein said product is stored and neutralized at a temperature of between about 40° and 85° F.
Claim 18
Dependent Claim
16 words
The method of claim 12 wherein said storage temperature is between about 40° and 60° F.
Claim 19
Dependent Claim
16 words
The method of claim 12 wherein said neutralization temperature is between about 40° and 60° F.
Claim 20
Dependent Claim
42 words
The method of claim 11 wherein said acidic aqueous liquor contains an acid selected from the group consisting of hydrochloric acid, malic acid, a tartaric acid, lactic acid, gluconic acid, acetic acid, sulfuric acid, a phosphoric acid, citric acid, and mixtures thereof.
Claim 21
Dependent Claim
11 words
The method of claim 15 wherein said acid is hydrochloric acid.
Claim 22
Dependent Claim
22 words
The method of claim 11 wherein the level of molecular oxygen under said storage conditions does not substantially exceed about 25 ppm.
Claim 23
Dependent Claim
16 words
The method of claim 17 wherein the oxygen concentration does not substantially exceed about 10 ppm.
Claim 24
Dependent Claim
24 words
The method of claim 11 wherein any head space above said acidic aqueous liquor is filled with an inert gas or is under vacuum.
Claim 25
Dependent Claim
15 words
The method of claim 19 wherein said inert gas is nitrogen or carbon dioxide gas.
Claim 26
Dependent Claim
25 words
The method of claim 11 wherein said neutralizing agent is an alkali metal or alkaline earth metal hydroxide, oxide, carbonate, bicarbonate, sesquicarbonate, or mixtures thereof.
Claim 27
Dependent Claim
11 words
The method of claim 21 wherein said agent is sodium hydroxide.
Claim 28
Dependent Claim
12 words
The method of claim 21 where said alkaline earth metal is calcium.
Claim 29
Dependent Claim
11 words
The method of claim 23 wherein said agent is calcium hydroxide.
Claim 30
Dependent Claim
18 words
The method of claim 11 wherein said product is stored for a time not exeeding about one year.
Claim 31
Dependent Claim
40 words
The method of claim 11 wherein the density of said aqueous acidic liquor is controlled to be about the same or slightly higher than the density of said stored product for suppressing crushing of said product during said storage thereof.
Claim 32
Dependent Claim
22 words
The method of claim 11 wherein said product is stored in its as-picked natural form, in subdivided solid form or mixtures thereof.
Claim 33
Dependent Claim
30 words
The method of claim 1 wherein said edible horticultural product is selected from the group consisting of tomatoes, carrots, peas, corn, beans, potatoes, turnips, asparagus, apples, pears, peaches, and avocados.
Claim 34
Dependent Claim
10 words
A method of claim 28 wherein said product comprises tomatoes.
Claim 35
Dependent Claim
17 words
The method of claim 11 wherein the pH of said liquor is not greater than about 1.60.
Claim 36
Dependent Claim
17 words
The method of claim 29 wherein the pH of said liquor is not greater than about 1.40.
Claim 37
Dependent Claim
23 words
The method of claim 31 wherein said product comprises tomatoes and the pH of said liquor is from about 1.0 to about 1.35.
Claim 38
Dependent Claim
14 words
The method of claim 32 wherein the pH is between about 1.25 and 1.35.
Claim 39
Dependent Claim
20 words
The method of claim 29 wherein said neutralizing agent is sodium hydroxide and said acidic aqueous liquor contains hydrochloric acid.
Claim 40
Independent Claim
100 words
A method for the preservative storage of tomatoes which comprises: storing said tomatoes in an acidic aqueous liquor at a temperature of between about 40° and 85° F., the pH of said liquor being between about 1.0 and about 1.35 and the oxygen concentration being not substantially above about 25 ppm to retard spoilage of said stored tomatoes; and at least partially neutralizing said tomatoes at a temperature of between about 40°-85° F. with a neutralizing agent at the termination of said storage to raise the pH of said tomatoes to an acceptable level for use of said stored tomatoes.
Claim 41
Independent Claim
100 words
A method for the preservative storage of tomatoes which comprises: storing said tomatoes in an acidic aqueous liquor at a temperature of between about 40° and 85° F., the pH of said liquor being between about 1.0 and about 1.35 and the oxygen concentration being not substantially above about 25 ppm to retard spoilage of said stored tomatoes; and at least partially neutralizing said tomatoes at a temperature of between about 40°-85° F. with a neutralizing agent at the termination of said storage to raise the pH of said tomatoes to an acceptable level for use of said stored tomatoes.
Claim 42
Dependent Claim
23 words
The method of claim 35 wherein said acidic aqueous liquor is rendered acidic with hydrochloric acid and said neutralizing agent is sodium hydroxide.
Claim 43
Dependent Claim
23 words
The method of claim 35 wherein said tomatoes are stored for a time ranging from between about one week and about one year.
Claim 44
Dependent Claim
16 words
The method of claim 35 wherein the oxygen concentration does not substantially exceed about 10 ppm.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-01-17 | 1986-07-19 | 1987-01-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-01-17 | 1990-07-19 | 1991-01-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-01-17 | 1994-07-19 | 1995-01-18 | $7700.00 | Window Closed / Lapsed |