WO2005000369A1 - Absorber composition for ethylene control - Google Patents

Absorber composition for ethylene control Download PDF

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Publication number
WO2005000369A1
WO2005000369A1 PCT/IB2003/003463 IB0303463W WO2005000369A1 WO 2005000369 A1 WO2005000369 A1 WO 2005000369A1 IB 0303463 W IB0303463 W IB 0303463W WO 2005000369 A1 WO2005000369 A1 WO 2005000369A1
Authority
WO
WIPO (PCT)
Prior art keywords
potassium permanganate
composition
comprised
ethylene
diatomite
Prior art date
Application number
PCT/IB2003/003463
Other languages
French (fr)
Inventor
Larry Shy
Barry Smith
Dan Eyde
Original Assignee
World Wide Sales Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by World Wide Sales Inc. filed Critical World Wide Sales Inc.
Priority to PCT/IB2003/003463 priority Critical patent/WO2005000369A1/en
Priority to AU2003249473A priority patent/AU2003249473A1/en
Publication of WO2005000369A1 publication Critical patent/WO2005000369A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • 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
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • 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
    • A23L3/3409—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 gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3418—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 gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23L3/3427—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 gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/013—Deodorant compositions containing animal or plant extracts, or vegetable material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Definitions

  • the present invention refers to a new absorber composition provided for the control of ethylene gas in fruit and vegetable ripening applications and, more generally, in the control of volatile organic compounds of the type from the general class of organic components which can oxidize into inoffensive products.
  • the object of the invention is to obtain a composition capable of being kept active for a significantly longer period of time, practically twice as long, than with conventional absorber compositions.
  • the absorber composition proposed by the invention significantly lengthens the efficacy or useful life in the control of odors, specifically remaining active for at least 30 days.
  • the invention consists of using diatomite as a substrate in replacement of the classic zeolites . Specifically, it has been foreseen that diatomites participate in the composition at a ratio comprised between 80 and 90%, while the rest is potassium permanganate. The optimal results of the invention are due to the high porosity of diatomite.
  • Diatomite is a sedimentary siliceous rock mainly composed of diatom bone remains of diatoms, which in turn consist of a microscopic, unicellular aquatic plant related to algae. Specifically, each diatom consists of a small membrane and internal structure surrounded by a shell or sample of concentrated opaline silica from nearby waters. Analysis shows a latticework structure which is porous and chemically inert. This unusual structure has a low density, high absorption capacity, large surface area and low thermal conductivity. Diatomite deposits are the result of the accumulation of diatoms in large shallow basins with a sufficient contribution of soluble silica.
  • a dry mixture of a diatomite substrate and potassium permanganate is carried out until obtaining a uniform product, the desired amount of water is added while blending the mixture .
  • Permanganate must be in solution to be effective, it having been experimentally proven that dry permanganate is ineffective in the reduction of ethylene concentrations.
  • An improvement in the composition is obtained by means of the optional addition of calcium chloride or another deliquescent salt, which has the effect of increasing water retention of the material. This is useful in low humidity applications where the drying of the material could cause an activity reduction. The following tests have been carried out with these raw materials :
  • the standard test was placing one ripe avocado in a one gallon sealed plastic container, with a standard amount of ethylene control agent.
  • a sample was taken by using an ethylene sampling tube to aspirate a known volume through the tube. The color change of the tube indicates the ethylene concentration.
  • the Containers were opened after each sampling and thoroughly vented. Sampling frequency was one sample per container per 24 hours.
  • Several different samples of control agents were compared using equivalent amounts of diatomite and zeolite based materials.
  • PRODUCT CONTAINING 20% POTASSIUM PERMANGANATE (DRY BASE) .
  • 20 grams of potassium permanganate, 80 grams of 6-8 meshwork diatomites and 70 grams of water were used. This material is dry, it shows no free moist surface. The • practical results were equivalent to those of the previous case.
  • PERMANGANATE (DRY BASE) . 20 grams of potassium permanganate, 5% calcium chloride,

Abstract

With a special application for the control of ethylene gas in fruit and vegetable ripening processes, consisting of a diatomite and potassium permanganate mixture, which is first mixed dry until producing a uniform product, and subsequently mixed with water, the diatomite participating at ratios comprised between 80 and 90%, and the potassium permanganate at a ratio comprised between 1 and 50%, such that the former constitutes a highly absorbent substrate for the latter, which permits increasing the amount of the latter and, accordingly, also increasing the activity of the composition. Said composition can optionally contain calcium chloride at a ratio comprised between 1 and 15% in order to improve the effect or increase of water retention of the composition.

Description

ABSQRBER COMPOSITION FOR ETHYLENE CONTROL
DESCRIPTION
OBJECT OF THE INVENTION The present invention refers to a new absorber composition provided for the control of ethylene gas in fruit and vegetable ripening applications and, more generally, in the control of volatile organic compounds of the type from the general class of organic components which can oxidize into inoffensive products. The object of the invention is to obtain a composition capable of being kept active for a significantly longer period of time, practically twice as long, than with conventional absorber compositions.
BACKGROUND OF THE INVENTION The effects of ethylene gas in the ripening and eventual decomposition of fruits and vegetables are known and abundantly documented. The use of potassium permanganate as an oxidizing agent has been known for many years, and in this aspect it is worth mentioning US Patent 552,142, granted in 1895, that is, over more than 100 years ago, which foresaw using a mixture between calcium chloride and potassium permanganate as an odor absorber means . US Patent 3,049,399 discloses a composition and method for deodorizing the air, in which potassium permanganate is also used, but in this case by impregnating an absorbent inorganic actived water adsorbing substrate. A more recent patent with a more general current use is
US Patent 5,278,112, which also maintains the use of potassium permanganate, but in this case impregnating, in other words using as a substrate, zeolites. Currently, the overwhelming majority' of ethylene control agents internationally manufactured and sold, are based on this US Patent, that is to say that they use zeolites as a substrate, which are impregnated with potassium permanganate and other additives, where applicable. The practical results of this solution, that is to say the absorber efficacy of this type of compositions, can be cited at approximately 15 days of exposure, after which time the composition becomes ineffective.
DESCRIPTION OF THE INVENTION By means of the use of a new substrate, the absorber composition proposed by the invention, also starting with the use of potassium permanganate, significantly lengthens the efficacy or useful life in the control of odors, specifically remaining active for at least 30 days. More specifically, the invention consists of using diatomite as a substrate in replacement of the classic zeolites . Specifically, it has been foreseen that diatomites participate in the composition at a ratio comprised between 80 and 90%, while the rest is potassium permanganate. The optimal results of the invention are due to the high porosity of diatomite. This porosity makes them capable of absorbing up to 100% of water (based on dry weight) and yet not have free water on the surface, which permits applying a larger amount of potassium permanganate in the solution and, accordingly, obtaining better activity. According to another one of the features of the invention, it has been foreseen that calcium chloride be added to said two basic raw materials, diatomite and potassium permanganate, at a ratio comprised between 1 and 15%, at the expense of a reduction in the same amount of diatomites.
PRACTICAL EMBODIMENT OF THE INVENTION Diatomite is a sedimentary siliceous rock mainly composed of diatom bone remains of diatoms, which in turn consist of a microscopic, unicellular aquatic plant related to algae. Specifically, each diatom consists of a small membrane and internal structure surrounded by a shell or sample of concentrated opaline silica from nearby waters. Analysis shows a latticework structure which is porous and chemically inert. This unusual structure has a low density, high absorption capacity, large surface area and low thermal conductivity. Diatomite deposits are the result of the accumulation of diatoms in large shallow basins with a sufficient contribution of soluble silica. A dry mixture of a diatomite substrate and potassium permanganate is carried out until obtaining a uniform product, the desired amount of water is added while blending the mixture . Permanganate must be in solution to be effective, it having been experimentally proven that dry permanganate is ineffective in the reduction of ethylene concentrations. An improvement in the composition is obtained by means of the optional addition of calcium chloride or another deliquescent salt, which has the effect of increasing water retention of the material. This is useful in low humidity applications where the drying of the material could cause an activity reduction. The following tests have been carried out with these raw materials :
The standard test was placing one ripe avocado in a one gallon sealed plastic container, with a standard amount of ethylene control agent. A sample was taken by using an ethylene sampling tube to aspirate a known volume through the tube. The color change of the tube indicates the ethylene concentration. To simulate realistic conditions, and to prevent the buildup of C02 gas, which could inhibit ethylene production, the Containers were opened after each sampling and thoroughly vented. Sampling frequency was one sample per container per 24 hours. Several different samples of control agents were compared using equivalent amounts of diatomite and zeolite based materials. EXAMPLE 1.-
COMPOSITION CONTAINING 12% POTASSIUM PERMANGANATE (KMn04) DRY BASE. 12 grams of potassium permanganate, 88 grams of 6-8 meshwork diatomites and 70 grams of water were used. This material was tested and compared to the material based on classic zeolites, resulting in a useful life in the range of 30 days or more, in other words, more than twice as long as that obtained with said zeolites.
EXAMPLE 2.-
PRODUCT CONTAINING 20% POTASSIUM PERMANGANATE (DRY BASE) . In this case, 20 grams of potassium permanganate, 80 grams of 6-8 meshwork diatomites and 70 grams of water were used. This material is dry, it shows no free moist surface. The • practical results were equivalent to those of the previous case.
EXAMPLE 3.-
PRODUCT CONTAINING 5% CALCIUM CHLORIDE AND 20% POTASSIUM
PERMANGANATE (DRY BASE) . 20 grams of potassium permanganate, 5% calcium chloride,
75% diatomite and 70 grams of water were used. The results were similar to those in Example 1, noting an increase in the water retention capacity of the composition. Lastly, it is necessary to indicate that it has been shown that placing the absorber composition inside of a Tyvek® bag does not reduce efficacy.

Claims

1.- An absorber composition for odor control which, especially designed for the control of ethylene gas in fruit and vegetable ripening. Comprised of a diatomite and potassium permanganate mixture.
2.- An absorber composition for ethylene control according to claim 1, comprising diatomites at a ratio comprised between 80 and 90%, whereas the potassium permanganate is comprised between 1 and 50%.
3. An absorber composition for ethylene control according to claim 1, comprising diatomites, potassium permanganate and a deliquescent material which calcium chloride is one.
4.- An absorber composition for ethylene control according to claim 3, comprising diatomites at a ratio comprised between 75 and 90%, potassium permanganate at a ratio comprised between 1 and 50%, and deliquescent material like calcium chloride at a ratio comprised between 1 and 15%.
5.- Any absorber composition for ethylene control using a deliquescent mineral like calcium chloride to attract water back to the absorbent to increase its efficiency or extend its useful life.
PCT/IB2003/003463 2003-06-30 2003-06-30 Absorber composition for ethylene control WO2005000369A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/IB2003/003463 WO2005000369A1 (en) 2003-06-30 2003-06-30 Absorber composition for ethylene control
AU2003249473A AU2003249473A1 (en) 2003-06-30 2003-06-30 Absorber composition for ethylene control

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2003/003463 WO2005000369A1 (en) 2003-06-30 2003-06-30 Absorber composition for ethylene control

Publications (1)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8152902B2 (en) 2009-09-30 2012-04-10 Cellresin Technologies, Llc Packaging material such as film, fiber, woven and nonwoven fabric with adsorbancy
WO2013187895A1 (en) * 2012-06-14 2013-12-19 Empire Technology Development Llc Multi-functional filtrate materials for adsorbing ethylene gas
US20140272039A1 (en) * 2013-03-15 2014-09-18 Multisorb Technologies, Inc. Reactive ethylene absorber
EP2965623A1 (en) 2014-07-09 2016-01-13 Sabanci Universitesi Food packaging material with antibacterial, ethylene scavenging and barrier properties
KR101754269B1 (en) 2016-08-10 2017-07-19 김인숙 Manufacturing method of deodorant containing diatomite wherein deodorizing effect and convenience of storage are improved, and a deodorant thereby
KR101754266B1 (en) 2016-08-10 2017-07-19 김인숙 Manufacturing method of antibiosis deodorant using firing diatomite, and a deodorant thereby
WO2018011666A1 (en) 2016-07-11 2018-01-18 Stora Enso Oyj Ethylene scavenging material suitable for use in packages and process for manufacturing thereof
FR3077563A1 (en) * 2018-02-07 2019-08-09 Nano4 POLYMERIC FILM FOR FOOD PACKAGING
WO2023129067A1 (en) 2021-12-28 2023-07-06 Sabanci Üniversitesi A polymeric material for preserving the freshness of food products

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US552142A (en) * 1895-12-31 Austin m
EP0071533A2 (en) * 1981-07-27 1983-02-09 L'Institut National Polytechnique de Toulouse (I.N.P.) Product for ethylene decay in food storage rooms
FR2535610A1 (en) * 1982-01-28 1984-05-11 Ass Rech Devel Amelio Product enabling the deodorisation of various premises and enclosed areas
US4535072A (en) * 1982-09-14 1985-08-13 Nihon Sanso Kabushiki Kaisha Absorbent for treating gases containing the materials used for semiconductor products and process of treating such gases with the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US552142A (en) * 1895-12-31 Austin m
EP0071533A2 (en) * 1981-07-27 1983-02-09 L'Institut National Polytechnique de Toulouse (I.N.P.) Product for ethylene decay in food storage rooms
FR2535610A1 (en) * 1982-01-28 1984-05-11 Ass Rech Devel Amelio Product enabling the deodorisation of various premises and enclosed areas
US4535072A (en) * 1982-09-14 1985-08-13 Nihon Sanso Kabushiki Kaisha Absorbent for treating gases containing the materials used for semiconductor products and process of treating such gases with the same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8152902B2 (en) 2009-09-30 2012-04-10 Cellresin Technologies, Llc Packaging material such as film, fiber, woven and nonwoven fabric with adsorbancy
WO2013187895A1 (en) * 2012-06-14 2013-12-19 Empire Technology Development Llc Multi-functional filtrate materials for adsorbing ethylene gas
US20140272039A1 (en) * 2013-03-15 2014-09-18 Multisorb Technologies, Inc. Reactive ethylene absorber
EP2965623A1 (en) 2014-07-09 2016-01-13 Sabanci Universitesi Food packaging material with antibacterial, ethylene scavenging and barrier properties
US9332751B2 (en) 2014-07-09 2016-05-10 Sabanci Universitesi Food packaging material with antibacterial, ethylene scavenging and barrier properties
WO2018011666A1 (en) 2016-07-11 2018-01-18 Stora Enso Oyj Ethylene scavenging material suitable for use in packages and process for manufacturing thereof
US11459159B2 (en) 2016-07-11 2022-10-04 Stora Enso Oyj Ethylene scavenging material suitable for use in packages
KR101754269B1 (en) 2016-08-10 2017-07-19 김인숙 Manufacturing method of deodorant containing diatomite wherein deodorizing effect and convenience of storage are improved, and a deodorant thereby
KR101754266B1 (en) 2016-08-10 2017-07-19 김인숙 Manufacturing method of antibiosis deodorant using firing diatomite, and a deodorant thereby
FR3077563A1 (en) * 2018-02-07 2019-08-09 Nano4 POLYMERIC FILM FOR FOOD PACKAGING
WO2019154860A1 (en) * 2018-02-07 2019-08-15 Nano4 Polymer film for food packaging
WO2023129067A1 (en) 2021-12-28 2023-07-06 Sabanci Üniversitesi A polymeric material for preserving the freshness of food products

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