CA2109418A1 - Glycine anhydride dimethylol as a biocide and preservative - Google Patents

Glycine anhydride dimethylol as a biocide and preservative

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Publication number
CA2109418A1
CA2109418A1 CA002109418A CA2109418A CA2109418A1 CA 2109418 A1 CA2109418 A1 CA 2109418A1 CA 002109418 A CA002109418 A CA 002109418A CA 2109418 A CA2109418 A CA 2109418A CA 2109418 A1 CA2109418 A1 CA 2109418A1
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CA
Canada
Prior art keywords
substance
glycine anhydride
product
dimethylol
anhydride dimethylol
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.)
Abandoned
Application number
CA002109418A
Other languages
French (fr)
Inventor
Phillip A. Berke
William E. Rosen
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.)
ISP Chemicals Products Inc
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2109418A1 publication Critical patent/CA2109418A1/en
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A23L3/3544—Organic compounds containing hetero rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plant Pathology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Dermatology (AREA)
  • Polymers & Plastics (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Food Science & Technology (AREA)
  • Water Supply & Treatment (AREA)
  • Birds (AREA)
  • Microbiology (AREA)
  • Nutrition Science (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Communicable Diseases (AREA)
  • Oncology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The use of glycine anhydride dimethylol, also known as 1,4-bis(hydroxymethyl)-2,5-piperazinedione, comprising formula (I) to kill microorganisms present in or on a host substance and to preserve products susceptible to contamination by a variety of microorganisms is disclosed.

Description

WO 9~19212 i~ PCr/US92/03442 GLYCINE ANHYDRIDE DIMETHYLOL
AS A BIOCIDE AND PRESERVATIVE

- BACKGROUND ~)F THE INVENTION
1. Technical Field of the Invention This invention rela~es ~o the use of glycine anhydride dime~hylol, as a biocide and an antimicrobial a~ent to kill microorganisms present in or on 5 substances and to preserve a variety of substances susceptible to microb;al contamination.
2. Description of the Priorart Glycine anhydride dimethyloi, also known as 1 ,~bis(hydroxymethyl)-2,5-piperazinedione is a known chemical compound prepared by reacting 10 glycine anhydride, als~ referred to as 2,5-piperazinedione with formaldehyde according to the following formula:

H
~N~"O ~N~,~O
~,~NJ ~ 2CH20 ~ ~,~NJ

H

See, e.g. Cherbuliez et al., Helv. Chim. Octa, 5, 678, 688 (1923).

SUMMARY OF THE INVFNTION
It is an object of the invention to provide a method for killing microorganisms present in or on a host substance by administering to the host an effective biocidal amount of glycine dimethylol anhydride.
It is a further object of the invention to provide a method for preserving products susceptible to contamination by microorganisms by incorporating into the product an antimicrobial effective amount of glycine anhydride dirnethylol.
It is a further 9bject of the invention to provide preserved products~
that is products which have been protected against contamination by WO 92/19212 PCr/lJS~2/~3442 h ~ 8 .
microorganisms, containing ~Iycine anhydride dimethylol in an amount which is e~fective to preserve the product against contamination by microorganisms.
O~her objects and advantages of the invention will be evident to those 5 of skill in the art upon review of the detailed description which ~ollows.

DETAILED DESCRIPTION OF THE
PREFERRED EMBODIMENTS
This invention is based upon the discovery that g~ycine anhydride dimethylol, also known as 1,4-bis(hydroxymethyl)-2,5-piperazinedione, 10 represented by ~he formula:

I
N ~O

~ \N/

exhibits biocidal activity against a wide range of microorganisms, includirlg bacteria, yeast and mold. This compound, therefore, is an effective biocidal agent which kills microorganisms present in or on a hos~ substance and 20 inhibits microbial growth in or on a variety of substances and products, whether they be solid, liquid or emulsion form. Such products include, but are not limited to, cosmetics, foodstuffs, pharmaceuticals, paints, cutting oils or fluids, agricultural products, oil drilling fluids, lubricants, paper industry products, embalming solutions, cold sterilized medical and dental 25 equipment, cooling tswers, fabric impregnation, latexes, swimming pools, inks, household disinfectants, waxes and polishes, toilet bowi cleaners, bathroom cleaners, laundry detergents, soaps, wood preservatives, hospital and medical antiseptic and adhesives. Of these products, fooàstuffs, pharmaceu~icals, cosrnetic and personal hygiene products such as shampoos 30 are of particular interest.

WO 92/1~21~ 8 PC r/US9~03~

Other uses of glycine anhydride dimethylol according to the invention include industrial uses where the compound is used to control microbial growth, such as for slime control in tl~e effluent of paper mills.
By virtue of its biocidal activity, glycins anhydride dimethylol can be 5 used to kill microorganisms which have contaminated a host substanoe or as a preservatiYe to inhibit and prevent growth of microorganisms in substances susceptible ~o microbial grovvth. The compound is also effective - in disinfecting and/or sterilizing surfaces prone to contamination by microorganisrns. The effective amount of glycine anhydride dimethylol 10 required will, of course, vary depending upon the mode of use, e.g., as a bioGidal agen~ to kill an established colony of microorganisrn or as a preservative to inhibit grovvth of microorganisms, to which it is directed.
Those of skill in the art will have no difficulty in determining the re~uisite effective amounts for particular uses.
When treating a host substance. the glycine anhydride dimethylol can be administer~d thereto as a solid powder, in aqueous solution or in an emulsion alone or with other ingredients, including other biocides and/or medicaments. The amount of glycine anhydride dimethylol required to be incorporated into a product for preservation will also vary dependin~ upon 20 the product being protected and the environment of use. Generally,products containing less than about 1.0% by weight of glycine anhydride dimethylol will be effectively protected from microbial contamination in most environments. Principally for economic reasons, eoncentrations less than about 0.5/~ by weight are preferred. Those of skill in the art will have little25 difficulty in selècting specific amounts required for particular uses based upon the infotmation contained herein, especially in the examples.
In addition to glycine anhydride dimethylol, other conventional ingredients may be incorporated into the product requiring preservation, including other antimicrobial a~ents, suspending agents, wetting agents, 30 anti-scaling a~ents, corrosion inhibitors and pH conlrol agents. The selection of the particular addition ingredients, if any, will depend upon the particular product requiring preservalion.

WO 92/19212 P~/U~;~2~3442 2 1 ~ 4 -When blending with the product to be preserved, the glycine anhydride d;methylol may be incorporated as a solid powder or in aquesus solution. The powder is the preferred form since it is easier to handle than a liquid. When the application calls for a liquid formulation, the powder can S be readily dissolved in aqueous media. The glycine anhydride dimethylol may be blended into the product as the sole antimicrobial agent or as part of an antimicrobial system with other antimicrobial agents. Such systems are particularly effective when it is necessary to preserve a product against a wide range of microorganisms. By careful selsction of the antimicrobial ayents in the system, antimicrobial activity against a particular group of microorganisms can be optimized for a particular product. When using an antimicrobial system it is further advantageous ~n incorporate the antimicrobial agents in a common solvent, such as propylene glycol, which als~ exhibits antimicrobial activity and so serves the dual function of solYent -and antimicrobial asent.
This invention thus provides an effective means ~or preserving substances susceptible to microbial oontamination by inhibiting growth of bacterial, yeast and mold. The compound of the invention is readily incorporated into a variety of forms including liquids, solids and emulsions.
To further illustrate the various aspects of the invention, the following examples are provided. However, it is to be understood that their purpose is entirely illustrative and in no way intended to limit the SCOpB of the inv~ntion. In the examples, all percentages are given by weight unless otherwise noted.

ExamDle I
Preparation of glycine anhydride dimethylol.
To a stir!ed slurry of 11-4 9. 10-1 mole) of glycine anhydride in 41.0 ml. of water was added 16-2 9. (0-2 mole) of 37% aqueous formaldehyde.
Addition of 0.10 9. of 10% aque~us sodium hydroxide solution caused the suspended s91ids to dissolYe, followed by formation of a heavy white precipitate. The mixture was heated to 70C, by which time all solids Wo92~19212 ~ i 8 Pcr/US92/03442 dissolved. On cooling to room temperature, white crystals separated . The crystals were collected, washed with cold water, and dried in vacuum at 1 00C for 1 hour. The white crystalline product, glycine anhydride dimethylol weighed 12.6 9. (72.4% yield), m.p. 185-188C dec. Anal.
Calcd. for C~H1oN204 (174.16): N, 16.09. Anal. Found: N, 16.17.
. ' ' ~'', ExamDle 2 Microbiological Activity A. Minimum Inhibi~ory Concentration (MIC) Aqueous solutions of 1% glycine anhydride dirnethylol were serially diluted with sterile distilled water, and aliquots of di~f2rent coneentrations were mixed with equal volumes of inoculated culture rnedium. AOAC broth was used for the bacterial culture media, and Sabourand Liquid Medium was used for the yeast and mold cultures. The mixtures of glycine anhydride dirn~thylol s~lution and culture media were incubated at 35C for 48 hours for bacteria and yeas~, and at 26~C for 7 days for mold. Microbial growth or no growth were determined by visual inspection for cloudiness. The MIC
for a given microorganism was the lowest concentration of antimicrobial that remained olear ~fter the incubation period. Results are as foilows:
Bacteria MIC
Gram-Ne~. Pseudomonas aeru~inosa ATCC 9027 310ppm Gram-Pos. Staphylococcus aureus ATCC 653B 31ûppm Yeast Candida albicans ATCC 10231 310ppm Mold Asper~illusni~er ATCC 1~404 2SOOppm B. Challenge tests on a cosmetic emulsion A typical cosmetic ernulsion was prepared for microbiologica challenge testing. The emulsion was prepared in four different variationS:
with no preservatiYe added, with 0.05% glycine anhydride dimethylol, with 0.10% glycine anhydride dimethylol, and with 0.20;o glycine anhydride dirnethylol. The formulation used for challenge testing was as follows:

WO 9~/lg212 PCrJUS~2/03442 21~94i8 6 .`"

Phase A %WNV
Water, Demineralized 67.90 67.85 67.8067.70 Triethanolamine, 99% 1.00 1.00 1.00 1.00 Phase B
Laneth-5 land) Ceteth-5 land) Olet~-5 land~ Steareth-5 0 50 0 50 0.50 0 ~0 Mineral Oil 2.50 2.50 2.50 2.50 Stearic Acid, XXX 5,00 5 00 5.00 5.00 Cetyl Alcohol 1.00 1.00 1.00 1.00 10 Glycer~l Steara~e land) PEG-100 Steara~e 1.50 1.50 1.50 1.50 E~h~ ohwrw Citric Acid ~30% Solution) 0.600.60 0.60 0.60 Pha$e D
Water, Demineralized 20.0020.00 20.00 20.00 Glycine Anhydride Dimeth~lol lGAD) _ Q.Q5 0.10 0.20 100.00 tOO.OO 100.00 100.00 Challenge tests were carried out using four different microorganisms, and microbial counts were made after incubating 24, 48, and 72 hours. The USP Antimicrobial Preservative Effectiveness Test ~UPS XXII Method) was 2û used with minor modifications.
MICROBIAL COUNTS, 24 HOURS

ND j0.05% ~ 0.10% 0.20%
. Preservative GAD GAD GAD
P. aeruginosa 9X1 o6 < 10 50 100 S- aureus2Xl 09 _ 4Xl 0- _ 5X1 ' - 2Xt o3 C. atbicans2.5X10~ 1 Xl 0 50 < 10 A. ni~er 5X1~ 500 < 10 ~10 _ ._. _ MICROBIAL COUNTS, 48 HOURS

No 0.05% 0.10% ¦ 0.20%
Preservative GAD GAD GAD
P. aeruginosa 1X10~ <10 15 1 60 S aureus 6X10~ 100 15 200 C albicans2X10' 1 X10' < 10 ~ 10 , 11 A, niger 4X10' ~10 < t O < 10 .

Wl:~ 92/19212 ~J ~ 8 PCI/US92~03442 MICROBIAL COUNTS, 72 HOURS

No 0.05%0.10% 0.20%
. _PreseNativ~ GAD GAD ~;AD
P. aeruginosa 1Xl03 ~10 ~10 c10 .
S. aureus 5X10 < 10 < 10 < 10 . . . . . _ _ ~:. albicans 2X1 O' 1 X103 < 10 < 10 _. ~ _ _ _ . .
A. niQer 3X10- <11) <10 <tO
_ _ , = . .

C. Challenge tests on a shampoo A typical shampoo was prepared both with and without glycine anhydrld~ dime~hylol, and then challenge tested with several microorganisms. The USP Antimicrobial Preservative Effectiveness Test.
10 (USPXXII Method) was used with minor modifications, with microbial counts made after 24, 48 and 72 hours. The same microorganisms tsame ATCC
numbers) were used a~ noted above.
The shampoo forrnulations were as follows:
Phase A %W/W
Water, Demineralized Ammonium Lauryl Sulfa~e 25.00 25.00 Cocamide DEA 6.50 6.50 Cocamideopropyl Botaine 5.00 5.00 20 Citric Acid, 30% Solution Phase Ç
Water, Deionized 20.00 20.00 Glycine Anhydride Dimethylol - 0.20 100.00 `100.00 t tJS to pH6 Pcr/US92/0344 21~ 118 - 8 -Microbial challenge test results were as follows:
MICROBIAL C:OUNTS, 74 HOURS

_ _ _ _ No Preservative_ 0.2% GAD ¦
P. aeruginosa _ 5X105 50 ~
S. aureus < 10 < 1 O _ C. albicans 2X104 c 10 . . ~ . _ I
A. niger 5Xt 0~ < 10 I :

MICROBIAL COUNTS, 48 HOURS

No Pre ervative 0.2% GAD ¦¦
P. aeruginosa _ 1X104 <1O
I S. aureus < 10 < 1 Q _ l¦
C. albicans 2X1 O' < 10 I.¦
A. niger lX105 . ~

MICROBIAL COUNTS, 72 HOURS

. . _ No Preservative ¦ 0.2% GAD
P. aeruginosa _ i ~0 c10 S. aureus < 10 < 10 C. albicans 2X104 1 < 10 A. niger D. Preservation of milk The microbial spoilage of whole milk aT room temperature was preYented by the incorporation of 0.16% glycine anhydride dimethylol. The 20 following series of tests were terminated after 59 days.

WO 92/19212 PCI /US~2/03442 2 ~ 1 8 g , . . . . _ . .
Preservativ~ Added Time to Spoilage _ to Who!e M;lk (i.e. development o~ odor, curdlin~, ~tc.) none 10 days ¦
. , .. .
0.16% _ 59+ ~ays 0.16% 59+ days_ _ ¦ 0.32%_ 59+ days 0 32% - 59 + days _ While the inv~ntion has been described in terms of certain preferred embodiments, one skilled in the art will readily ap~reciate that various 10 modifications, ohanges, omissions and substitutions may be made without departing from ~he spiri~ thereof. It is intended, therefore, that the present invention be limited solely by the scope of the following ciaims.

Claims (24)

What is claimed is:
1. A method of killing microorganisms in or on a host substance comprising administering to the substance an effective biocidal amount of glycine anhydride dimethylol of the formula:
2. The method as defined in Claim 1, wherein the glycine anhydride dimethylol is administered in aqueous solution.
3. The method as defined in Claim 1, wherein the glycine anhydride dimethylol is administered in an emulsion.
4. The method as defied in Claim 1, wherein the glycine anhydride dimethylol is administered as a powder.
5. The method as defined by Claim 1, wherein the glycine anhydride dimethylol is administered in conjunction with another biocidal agent.
6. A method for protecting a substance against contamination by microorganisms comprising incorporating in the substance an effective antimicrobial amount of glycine anhydride dimethylol for the formula:
7. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in an amount less than about 1.0% by weight.
8. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in an amount less than about 0.5% by weight.
9. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in solid form.
10. The method as defined by Claim 6, wherein said glycine anhydride dimethylol is incorporated into said substance in aqueous solution.
11. The method as defined in Claim 6, wherein said substance is a cosmetic product.
12. The method as defined in Claim 6, wherein said substance is a personal hygiene product.
13. The method as defined in Claim 12, wherein said personal hygiene product is a shampoo.
14. The method as defined in Claim 6, wherein said substance is a pharmaceutical product.
15. The method as defined in Claim 6, wherein said substance is a foodstuff.
16. The method as defined in Claim 6, wherein said substance is the effluent from a paper mill.
17. A preserved product comprising a substance susceptible to microbial contamination and an effective microbial growth Inhibiting amount of glycine anhydride dimethylol for the formula:
18. The product defined by Claim 17, wherein said glycine anhydride dimethylol is present in an amount less than about 1.0% by weight.
19. The product defined by Claim 18, wherein said glycine anhydride dimethylol is present in an amount less than 0.5% by weight.
20. The product defined by Claim 17, wherein said substance is a cosmetic.
21. The product defined by Claim 17, wherein said substance is a personal hygiene product.
22. The product defined by Claim 21, wherein said substance is a shampoo.
23. The product defined by Claim 17, wherein said substance is a pharmaceutical product.
24. The product defined by Claim 17, wherein said substance is a foodstuff.
CA002109418A 1991-05-01 1992-04-30 Glycine anhydride dimethylol as a biocide and preservative Abandoned CA2109418A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US694,252 1991-05-01
US07/694,252 US5244653A (en) 1991-05-01 1991-05-01 Glycine anhydride dimethylol as a biocide and preservative

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CA2109418A1 true CA2109418A1 (en) 1992-11-02

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EP (1) EP0583357A4 (en)
JP (1) JPH06507403A (en)
CN (1) CN1066170A (en)
AU (1) AU654192B2 (en)
BR (1) BR9205953A (en)
CA (1) CA2109418A1 (en)
CZ (1) CZ230193A3 (en)
MX (1) MX9201988A (en)
NO (1) NO933894L (en)
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US5244653A (en) 1993-09-14
US5593681A (en) 1997-01-14
AU654192B2 (en) 1994-10-27
EP0583357A4 (en) 1994-05-18
MX9201988A (en) 1992-11-01
CZ230193A3 (en) 1994-07-13
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ZA923063B (en) 1993-04-28
CN1066170A (en) 1992-11-18

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