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EP0596059A1 - Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage - Google Patents

Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage

Info

Publication number
EP0596059A1
EP0596059A1 EP93908878A EP93908878A EP0596059A1 EP 0596059 A1 EP0596059 A1 EP 0596059A1 EP 93908878 A EP93908878 A EP 93908878A EP 93908878 A EP93908878 A EP 93908878A EP 0596059 A1 EP0596059 A1 EP 0596059A1
Authority
EP
European Patent Office
Prior art keywords
chemical
oxidation
nitrogen
gases
noble
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP93908878A
Other languages
German (de)
English (en)
Inventor
Kevin C. Spencer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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 Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to EP02012889A priority Critical patent/EP1258522A2/fr
Publication of EP0596059A1 publication Critical patent/EP0596059A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds

Definitions

  • the present invention provides a method of controlling the oxidation of chemicals during storage using a noble gas, a mixture of noble gases or a gaseous mixture containing at least one noble gas. Description of the Background;
  • French Patent 1,339,669 discloses that argon may be used to render oxidizable chemicals of biological origin inert to oxidation because it desorbs oxygen.
  • this patent specifically states that oxygen must be removed for any inhibitory effect upon oxidation to be observed.
  • U.S. 3,143,471 a method is described whereby dry argon is used in the packaging of lyophilized pharmaceuticals, generally, wherein the sole object of the process is the displacement of water and oxygen from the packaging space.
  • inert or non-reactive atmospheres which can be either nitrogen or argon are recommended for packaging or storaging chemicals or chemical preparations such as oils (JP 3200568), polyacrylic acids (U.S. 4,622,425), N,N-dialkylaminopropyl compounds (JP 63077848), alpha-cyano-acrylic ester (JP 52097913, 85007609), vinylidene halide compounds (U.S. 3,957,892), sodium products (FR 2,261,518), chemical propellants (DE 3,007,712), medical solutions (U.S. 4,664,256), silicon wafers (U.S.
  • HEET CH 589403 AT 7505161, DE 2,437,812, IT 1040412, JP 51035583, JP 83040521
  • developer sheets JP 3057689, U.S. 5,064,070
  • photosensitive donor media U.S. 4,965,165
  • agricultural antiseptic suspensions JP 2104502
  • preparation or synthesis of chemicals under generally inert atmospheres in which the use of either nitrogen or argon without distinction is recommended include, as examples, purification and stabilization of catechol-containing proteins (U.S. 4,496,397), preparation of cosmetic dyes (U.S. 4,314,810), synthesis of peptides (FR 1,454,653, AU 6565762), synthesis of antibiotics (JP 58039650, JP 89039416).
  • an object of the present invention to provide a method for enhancing the stability of chemicals or chemical preparations during storage thereof.
  • a method of controlling the oxidation of chemicals or chemical preparations during at least a portion of storage thereof by contacting the same with a noble gas, a mixture of noble gases or a gaseous mixture containing at least one noble gas.
  • Figure 2 illustrates the absorptivity of Quercetin under different atmospheres of oxygen, nitrogen, argon, krypton and xenon at 25°C.
  • Figure 3 illustrates the absorptivity of Quercetin under different atmospheres of oxygen, nitrogen, argon, neon and air at 25°C.
  • Figure 4 illustrates the absorptivity of morphine sulfate under different atmospheres of oxygen, nitrogen and argon after 31 days of storage at ambient temperature.
  • Figure 5 illustrates the absorptivity of apomorphine hydrochloride under different atmospheres of oxygen, nitrogen and argon after 31 days of storage at ambient temperature.
  • Figure 6 illustrates the absorptivity of apomorphine hydrochloride under different atmospheres of oxygen, nitrogen and argon after 31 days of storage at ambient temperature.
  • Figure 7 illustrates the absorptivity of apomorphine hydrochloride under different atmospheres of nitrogen and argon after 31 days at ambient temperature.
  • Figure 8 illustrates the absorptivity of epinephrine hydrochloride under different atmospheres of nitrogen, argon, krypton and xenon after 31 days at ambient temperature.
  • Figure 9 illustrates the absorptivity of epinephrine hydrochloride under different atmospheres of nitrogen and xenon for 31 days and three and one-half months, respectively, for each.
  • Figure 10 illustrates the absorptivity of L-ascorbic acid under different atmospheres of oxygen and nitrogen.
  • HEET Figure 11 illustrates the absorptivity of L-ascorbic acid under different atmospheres of nitrogen, argon, krypton, xenon and neon after 30 days at ambient temperature.
  • Figure 12 illustrates the absorptivity of retinol under different atmospheres of nitrogen, argon, krypton and xenon after 3 months at ambient temperature in darkness.
  • Figure 13 illustrates the absorptivity of tetracycline hydrochloride under different atmospheres of air and nitrogen for 33 days and four months each, respectively.
  • Figure 14 illustrates the absorptivity of tetracycline hydrochloride under different atmospheres of air and neon for 33 days and four months each, respectively.
  • the present invention it has been surprisingly discovered that it is possible to directly affect the rate of oxidation of chemicals or chemical preparations. That is, in accordance with the present invention it has been discovered that certain gases can directly affect the oxidation rate of chemicals and not merely slow oxidation only as function of physical and inert displacement of oxygen.
  • the present invention is effected by contacting the chemicals or chemical preparations during at least a portion of storage thereof to a noble gas, a mixture of noble gases or a gaseous mixture containing at least one noble gas.
  • the present invention is predicated upon the discovery that by contacting chemicals or chemical preparations with an atmosphere containing a noble gas, a mixture of noble or a gaseous mixture containing at least one noble gas during at least a portion of storage it is possible to effectively control oxidation reactions which degrade such compounds or preparations.
  • noble gases are surprisingly more effective than nitrogen or other inert or non-reactive gases in actually and effectively controlling the oxidation of chemical compounds or chemical preparations.
  • the present invention is predicated upon a, heretofore, undiscovered property of noble gases in interfering with oxidation reactions of chemicals and chemical preparations during storage.
  • a method is also provided for inhibiting oxidation of chemicals or chemical preparations. Further, the present invention may be advantageously used at any time during storage of chemicals or chemical preparations.
  • noble gases possess a surprising ability to control, and specifically inhibit oxidation to a degree quite superior to that exhibited by nitrogen.
  • the use of noble gases instead of nitrogen confers additional stability to stored chemical products or chemical preparations.
  • the term "noble gas” generally includes argon, xenon, krypton or neon. While other noble gases, such as radon or helium may be used, the use of radon is generally impractical as it is dangerously reactive. While helium confers a positive benefit, and less than the other noble gases, and may be freely admixed with any other noble gas to advantage, its use is limited by its poor solubility in aqueous solutions and its tendency to dissipate by penetrating packaging materials. However, it is reiterated that the present invention is predicated upon the surprising discovery of the ability of all of the noble gases to control the oxidation of chemicals or chemical preparations.
  • atmospheres containing noble gases in quantities greater than those normally found in ambient air significantly improve storage characteristics and shelf-life of chemicals or chemical preparations. Further, the effective improvement is of wide practical utility and clear economic benefit.
  • any amount of noble gas above that found in normal atmospheric air may be used to advantage in the present invention.
  • argon is generally accepted as being present in the atmosphere in the amount of about 0.934% by volume.
  • neon, krypton and xenon are normally present in the atmosphere in amounts of 1.82 X 10 ⁇ 3 , 1.14 X 10" 3 and 8.7 X 10 ⁇ 6 , respectively, by % volume.
  • Advanced Inorganic Chemistry , Cotton and Wilkinson (Third Edition, Wiley).
  • any amount of noble gas may be used which is greater than that found in atmospheric air.
  • this amount is preferably at least 1% by volume, and is more preferably in excess of 1% by volume for argon.
  • krypton and xenon amounts generally used are at least 0.05% each, by volume. However, it is generally preferred that the amounts of neon, krypton and xenon used be greater than about 0.1% each, by volume.
  • any gas, mixtures of gases, liquid or mixtures of liquids may be used in accordance with the present invention as long as they contain an amount of at least one noble gas as described above. Preferably, however, they contain at least the preferred amounts noted above.
  • -lo ⁇ in addition to noble gases or noble gas mixtures, any gaseous mixture may be used in accordance with the present invention which contains at least one noble gas.
  • unpurified mixtures of gases from air separation plants such as about 90;10 Kr;Xe, and about 1:1 He:Ne, for example.
  • atmospheric pressures of from less than one to greater than 1 may be used.
  • it has been found acceptable to use quite low pressures such as those near vacuum conditions, such as, for example about 10 ⁇ 9 torr to very high pressures of about 100 atm or greater.
  • atmospheres ranging from about 0.5 to 20 atm, preferably about from 1 to 10 atm.
  • the effective stabilization is observed even when the noble gas-containing atmosphere contains other inert gases, such as nitrogen.
  • the effect appears to be directly related to the actual quantitative amount of noble gas present and available to the reactive sites on the subject chemical or chemical preparation.
  • the effect thereof is observed even when the noble gas- containing atmosphere contains other reactive gases including oxygen, carbon dioxide, water, or nitrous oxide.
  • diminution of the antioxidative effect is seen in direct consequence of the inclusion of these oxygen-containing gases, and is a direct, linear function of their concentration.
  • the maximum antioxidative effect of argon is seen when argon is present as 100% of the superimposed atmosphere (and effectiveness may be increased by increasing the relative molar concentration of argon by increasing pressure)
  • the minimal effect is observed when argon is present in concentrations only slightly greater than its normal concentration in air (0.1% by volume) admixed with any of oxygen, carbon dioxide, water or nitrous oxide.
  • the method is most effective when noble gas concentrations in excess of 50% of the atmosphere are used, preferably in excess of 90%, preferably in excess of 95% of the atmosphere.
  • the improvement of the present invention is generally noted for noble gas-containing atmospheres which might also contain other gases, except that reactive components of these other gases may promote oxidation and mask the desired effect.
  • reactive components of these other gases may promote oxidation and mask the desired effect.
  • complex mixtures of gases which include noble gases will promote oxidation less than similar mixtures which do not contain noble gases.
  • the antioxidation potential of the noble gases is of the order of:
  • the observed effectiveness of the noble gases is partially, but not wholly dependent, upon their relative solubility in the chemicals or chemical preparations treated.
  • the observed effectiveness of the noble gases is partially, but not wholly dependent, upon their relative ability to desorb oxygen or water from subject chemical preparations.
  • the effects of the noble gases may be either ameliorated or potentiated by the admixture of other gases thereto.
  • the observed improvement in accordance with the present invention is notable for noble-containing solutions, either aqueous or non-aqueous, when applied to retard oxidation, in a manner similar to the use of atmospheres.
  • the optimal method consists of saturating the solution with the desired gas by sparging or superimposition or by use of pressure or through introduction of cryogenic liquid.
  • cryogenic liquid composed of or containing noble gases, such as cryogenic argon
  • cryogenic nitrogen inert
  • carbon dioxide reactive
  • the quantative improvement in sh ⁇ lf-life may be observed is several times that observed with nitrogen, with the improvement being 25 to 100% being obtained with ease.
  • the preferred method of use of the present invention is to store the chemicals or chemical preparations under an atmosphere containing a noble gas, mixture of noble gases or gaseous mixture containing at least one noble gas which gases exhibit the best effect, and additionally storing in gas- and moisture-impermeable containers, storing at low temperatures and storing in containers which block incident light or other radiation.
  • any chemical or chemical preparation which is susceptible to oxidative degradation may be protected by the present invention.
  • such chemicals or preparations may include chemical reagents, deoxygenated solvents, reducing agents and catalysts.
  • storage temperatures of from about -20°C to about 60°C, preferably from about -10°C to about 30°C, may be used.
  • the progress of the oxidations were monitored either by ultraviolet/visible spectrophoto etry, or by spectrocolorimetry, or by direct visual observation, or by the production of a detectable product (detected chemically, or by gas chromatography/mass spectrometry, or by thin layer chromatography) , or by other standard means, depending upon the nature of the chemical oxidation to be measured.
  • the atmospheres tested include argon, xenon, krypton, neon, helium, nitrogen, oxygen, air, carbon dioxide, nitrous oxide, and decile mixtures of each possible pair and triad, and certain representative other combinations. Tests were conducted in the presence or absence of water vapor, light, temperature, and under differing conditions of concentration and pH. In certain cases, atmospheres were changed after a certain time period in order to observe changing effects. For instance, it was observed in every case of noble gas retardation of oxidation that replacing the noble gas-containing atmosphere with air or oxygen immediately produced the maximum degenerative effect, and that replacing the effective noble gas-containing atmosphere with nitrogen immediately ended the observed retardation effect.
  • nitrous oxide, carbon dioxide, air and oxygen produced degenerative oxidative effects, nitrogen diminished these effects to the extent that oxygen was excluded from the reaction, and the noble gases diminished the effect further. This further effect was evident even when oxygen was added in amounts greater than could be accounted for by the different desorptive ability of the various noble gases and nitrogen, and in amounts greater than could be accounted for by different solubilities of the gases in solution.
  • Vitamin Bl Specific Examples: Example 1: Quercetin
  • the 2 vials are stored at room temperature over the week-end (unprotected from light) .
  • Vial C/0 2 (see 09/13/91 QUERC01.WP) has turned orange, while vial C/N 2 is still yellow. No further color changes are observed on the following days. 2. Full Range Scans (900-190 nm) : 09/16/91
  • Purge cuvet 1 with 0 2 on-line for 30 s.
  • Purge cuvet 2 with N 2 on-line for 30 s.
  • Blank cuvet acrylic cuvet filled with 3 ml D.I. H 2 0. Using a 3cc syringe previously purged with 0 , transfer 3 ml from vial C/0 2 into cuvet 1.
  • Blank cuvet acrylic cuvet filled with 2.5 ml of TRIS buffer pH 9.0.
  • Label and stopper 5 acrylic cuvets with blue silicone (gas-tight) .
  • Label QT4Gn, where:
  • the gassing order is still: N 2 , Ar, Kr, Xe and finally 0 2 .
  • Blank cuvet acrylic cuvet filled with 2.5 ml of TRIS buffer pH 9.0.
  • the 100 ⁇ g/ml quercetin solution is stored in refrigerator (serum vial being wrapped in aluminum foil to prevent light degradation) .
  • Blank cuvet acrylic cuvet filled with 2.5 ml of TRIS buffer pH 9.0.
  • Stopper 1 acrylic cuvet with blue silicone (gas- tight) . Flush cuvet with on-line nitrogen for 1 min. Using a 3cc B-D syringe (purged with N 2 ) , transfer 2.5 ml of solution C into the cuvet. Run a full range scan (900-190 nm) of sample cuvet vs blank.
  • Bubble 3x3Occ of the appropriate gas through each vial Inject an additional lOcc of the appropriate gas to leave vial under positive pressure.
  • Gassing is done in the following order: N , Ne, Ar, Kr, Xe, Air, and finally 0 2 .
  • the lOcc vials are left on the lab bench at room temperature.
  • the vials are regularly observed visually for color changes.
  • Blank cuvet acrylic cuvet filled with 2.5 ml of TRIS buffer pH 9.0.
  • Figure 1 shows that following ABS at 400 nm will reveal the progressive oxidation of the molecule.
  • Figure 2 shows that nitrogen retards oxidation poorly compared to argon, and krypton and xenon inhibit oxidation much better than argon.
  • Figure 3 shows a replicate (differences between Figs. 2 and 3 are due to different start times) which shows additionally that neon inhibits about as well as argon. Since the solubilities of argon and neon are very different yet that of neon and nitrogen very similar, the activity is clearly at least partly independent of solubility.
  • Figure 9 demonstrates the same for nitrogen and xenon in comparing degree of oxidation after 1 month versus 3 1/2 months of storage.
  • Example 5 L-Ascorbic acid
  • Figure 10 shows the oxidative abscissal absorbance shift.
  • Figure 11 shows that preservation is in the order Kr>Ar>Ne>N 2 >Xe after 30 days.
  • Figure 12 shows the very great improvement obtained in storing retinol under noble gases compared with nitrogen.
  • diminution of absorbance in the 320-324 nm range is indicative of oxidation.
  • Figure 13 compares oxidation over this time period in an oxygen atmosphere versus a nitrogen atmosphere. Comparing Figure 13 with Figure 14 demonstrates clearly that a neon atmosphere provides greater protection.
  • the present invention is surprisingly effective in controlling oxidation of chemicals or chemical preparations or both in storage.
  • binary mixtures such as argon-krypton, krypton-neon, xenon-krypton or argon-neon, for example, ternary mixtures or even quaternary mixtures of noble gases may be used.
  • deoxygenated air generally means an oxygen content of less than about 15%, better yet less than about 10%, and more preferably less than about 5% by volume.
  • the gases or gas mixture may be introduced either in gaseous or liquid form. If liquid form, the noble gases may be used neat or dissolved in a suitable liquid gas such as liquid nitrogen.
  • the advantage of the present invention may be obtained even if the chemicals or chemical preparations are contacted with the gases of the present invention for only a portion of the storage period. However, it is generally preferably to effect such contact throughout the entire storage period.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

Procédé de limitation de l'oxydation d'un produit chimique ou d'une préparation chimique pendant son entreposage. Il consiste, pendant au moins une partie de la durée d'entreposage, à mettre les produits ou préparations chimiques en contact avec au moins un gaz noble, un mélange de gaz nobles ou un mélange gazeux renfermant au moins un gaz noble.
EP93908878A 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage Withdrawn EP0596059A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02012889A EP1258522A2 (fr) 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US86305692A 1992-04-03 1992-04-03
US863056 1992-04-03
PCT/EP1993/000802 WO1993020168A1 (fr) 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP02012889A Division EP1258522A2 (fr) 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage

Publications (1)

Publication Number Publication Date
EP0596059A1 true EP0596059A1 (fr) 1994-05-11

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP93908878A Withdrawn EP0596059A1 (fr) 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage
EP02012889A Withdrawn EP1258522A2 (fr) 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage

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EP02012889A Withdrawn EP1258522A2 (fr) 1992-04-03 1993-03-31 Procede de limitation, a l'aide de gaz nobles, de l'oxydation des produits chimiques pendant leur entreposage

Country Status (5)

Country Link
EP (2) EP0596059A1 (fr)
JP (1) JPH06507940A (fr)
AU (1) AU3950493A (fr)
CA (1) CA2102779A1 (fr)
WO (1) WO1993020168A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6320069B1 (en) * 1996-07-02 2001-11-20 Toray Industries, Inc. Production of optically active ketone
IT1301771B1 (it) * 1998-06-22 2000-07-07 Laffon Spa Procedimento di riempimento meccanico di un contenitore per prodotticosmetici.
WO2011075391A1 (fr) * 2009-12-15 2011-06-23 Schering Corporation Mode de préparation d'acadésine
US9119876B1 (en) 2015-03-13 2015-09-01 Par Pharmaceutical, Inc. Epinephrine formulations
US20170189352A1 (en) 2015-03-13 2017-07-06 Par Pharmaceutical, Inc. Epinephrine formulations
WO2019183416A1 (fr) 2018-03-23 2019-09-26 Nevakar Inc. Compositions et récipients d'épinéphrine
US20200197355A1 (en) * 2018-12-20 2020-06-25 Public Joint Stock Company "Scientific Industrial Centre "Borshchahivskiy Chemical-Pharmaceutical Pl Methods, compositions and containers for reducing solid form quercetin degradation and 2-(3,4-dihydroxybenzoyloxy)-4,6-dihydroxybenzoic acid toxic byproducts thereof
US20200197354A1 (en) * 2018-12-20 2020-06-25 Public Joint Stock Company "Scientific Industrial Centre "Borshchahivskiy Chemical- Pharmaceutical P Methods, compositions and containers for reducing solid form quercetin degradation and 2,4,6-trihydroxybenzoic acid toxic byproduct thereof
US11156623B2 (en) 2018-12-20 2021-10-26 Public Joint Stock Company “Scientific Industrial Centre Borshchahivskiy Chemical-Pharmaceutical Plant” Methods of monitoring safety of quercetin compositions

Citations (3)

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Publication number Priority date Publication date Assignee Title
FR1339669A (fr) * 1962-08-31 1963-10-11 Air Liquide Procédé de stabilisation de produits altérables à l'air
US4328249A (en) * 1981-01-30 1982-05-04 Life Savers, Inc. Method for treating gum base to improve shelf-life without need for antioxidants
DE3912153C1 (en) * 1989-04-13 1990-08-02 Christoph V. Dr.Rer.Nat. Stein Preventing deterioration of solns. by oxidn. - by feeding solns. in containers from which air has been expelled by injected protective gas

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JPS548840A (en) * 1977-06-22 1979-01-23 Suwa Seikosha Kk Time keeper using cell
JPS56161841A (en) * 1980-05-19 1981-12-12 Mitsubishi Petrochem Co Ltd Manufacture of composite oxide catalyst
DE3341513A1 (de) * 1983-11-17 1985-06-20 Hans 5462 Bad Hönningen Ziegeler Verfahren fuer korrosionsschutz und konservierung von sauerstoff und mit sauerstoff oxidierenden gegenstaenden, aller art und groesse
NZ235528A (en) * 1989-10-05 1992-12-23 Air Liquide Preservation of fresh edible plant products using an atmosphere containing nitrogen monoxide and/or argon
US5021251A (en) * 1990-07-23 1991-06-04 Borden, Inc. Process for preserving lemon juice utilizating a non-sulfite preservative
TW284788B (fr) * 1991-05-28 1996-09-01 L Air Liquide Soliete And Nyme Dour L Expl Des Proce
KR950006897B1 (ko) * 1991-07-04 1995-06-26 롱-쁠랑 쉬미 포화 탄화수소의 암모산화 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1339669A (fr) * 1962-08-31 1963-10-11 Air Liquide Procédé de stabilisation de produits altérables à l'air
US4328249A (en) * 1981-01-30 1982-05-04 Life Savers, Inc. Method for treating gum base to improve shelf-life without need for antioxidants
DE3912153C1 (en) * 1989-04-13 1990-08-02 Christoph V. Dr.Rer.Nat. Stein Preventing deterioration of solns. by oxidn. - by feeding solns. in containers from which air has been expelled by injected protective gas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9320168A1 *

Also Published As

Publication number Publication date
JPH06507940A (ja) 1994-09-08
WO1993020168A1 (fr) 1993-10-14
CA2102779A1 (fr) 1993-10-04
AU3950493A (en) 1993-11-08
EP1258522A2 (fr) 2002-11-20

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